DE19954228A1 - New epothilone derivatives used for treating e.g. malignant melanoma, breast carcinoma, psoriasis, multiple sclerosis and arthritis - Google Patents

New epothilone derivatives used for treating e.g. malignant melanoma, breast carcinoma, psoriasis, multiple sclerosis and arthritis

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Publication number
DE19954228A1
DE19954228A1 DE19954228A DE19954228A DE19954228A1 DE 19954228 A1 DE19954228 A1 DE 19954228A1 DE 19954228 A DE19954228 A DE 19954228A DE 19954228 A DE19954228 A DE 19954228A DE 19954228 A1 DE19954228 A1 DE 19954228A1
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Germany
Prior art keywords
ethenyl
dione
dihydroxy
tetramethyl
oxa
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Ceased
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DE19954228A
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German (de)
Inventor
Ulrich Klar
Wolfgang Schwede
Werner Skuballa
Bernd Buchmann
Jens Hoffmann
Rosemarie Lichtner
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Bayer Pharma AG
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Schering AG
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Priority to DE19954228A priority Critical patent/DE19954228A1/en
Priority to UA2001107395A priority patent/UA73118C2/en
Priority to PE2000000403A priority patent/PE20010116A1/en
Priority to ARP000102024A priority patent/AR023792A1/en
Priority to BR0010190-7A priority patent/BR0010190A/en
Priority to YUP-776/01A priority patent/RS51023B/en
Priority to JP2000615619A priority patent/JP4024003B2/en
Priority to DK00922826T priority patent/DK1173441T3/en
Priority to CNB008069786A priority patent/CN100368415C/en
Priority to PL351491A priority patent/PL210762B1/en
Priority to CZ20013885A priority patent/CZ299653B6/en
Priority to NZ514989A priority patent/NZ514989A/en
Priority to KR1020017013840A priority patent/KR100721488B1/en
Priority to AT00922826T priority patent/ATE440847T1/en
Priority to CA2371226A priority patent/CA2371226C/en
Priority to CA2651653A priority patent/CA2651653C/en
Priority to SK1551-2001A priority patent/SK286858B6/en
Priority to PT00922826T priority patent/PT1173441E/en
Priority to EA200101025A priority patent/EA011502B1/en
Priority to DE60042821T priority patent/DE60042821D1/en
Priority to IL14593800A priority patent/IL145938A0/en
Priority to PCT/IB2000/000657 priority patent/WO2000066589A1/en
Priority to MEP-139/08A priority patent/MEP13908A/en
Priority to AU43103/00A priority patent/AU772750C/en
Priority to MXPA01011039A priority patent/MXPA01011039A/en
Priority to SI200031044T priority patent/SI1173441T1/en
Priority to EEP200100568A priority patent/EE05292B1/en
Priority to ES00922826T priority patent/ES2331506T3/en
Priority to EP00922826A priority patent/EP1173441B1/en
Priority to US09/979,939 priority patent/US7125893B1/en
Priority to HU0201010A priority patent/HUP0201010A3/en
Priority to TW89108133A priority patent/TWI280962B/en
Priority to TW095145399A priority patent/TWI294292B/en
Publication of DE19954228A1 publication Critical patent/DE19954228A1/en
Priority to IL145938A priority patent/IL145938A/en
Priority to BG106053A priority patent/BG65601B1/en
Priority to NO20015278A priority patent/NO328149B1/en
Priority to ZA200109859A priority patent/ZA200109859B/en
Priority to HR20010892A priority patent/HRP20010892A2/en
Priority to HK02108204.3A priority patent/HK1046681B/en
Priority to US10/965,802 priority patent/US7645891B2/en
Priority to US11/214,988 priority patent/US7700621B2/en
Priority to JP2007104224A priority patent/JP4886578B2/en
Priority to CY20091101237T priority patent/CY1109768T1/en
Priority to US12/721,614 priority patent/US20100168179A1/en
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P35/00—Antineoplastic agents
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    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Abstract

Epothilone derivatives (I) are new. Epothilone derivatives of formula (I) are new. R1a, R1b = H, 1-10C alkyl, 6-12C aryl or 7-20C aralkyl (all optionally substituted) or R1a + R1b = (CH2)m or (CH2)-O-(CH2); m = 1-5; R2a = H, 1-10C alkyl, 6-12C aryl or 7-20C aralkyl (all optionally substituted), (CH2)raC equivalent to C-(CH2)pa-R26a, (CH2)raCH=CH-(CH2)pa-R26a or a group of formula (i) or (ii); R2b = (CH2)rbC equivalent to C-(CH2)pb-R26a, (CH2)rbCH=CH-(CH2)pb-R26a or a group of formula (iii) or (iv); n = 0-5; ra, rb = 0-4; pa, pb = 0-3; R3a = H or 1-10C alkyl, 6-12C aryl or 7-20C aralkyl (all optionally substituted); R3b = OH or OPG<14>; PG<14> = a protective group; R<14> = H, OR14a or hal; R14a = H, SO2-alkyl, SO2-aryl or SO<2>-aralkyl; R<4> = H, 1-10C alkyl, 6-12C aryl or 7-20C aralkyl (all optionally substituted), hal, OR<25> or CN; R<25> = H or a protective group PG<5>; R26a, R26b = H or 1-10C alkyl, 6-12C aryl or 7-20C aralkyl (all optionally substituted), 1-10C acyl or, if pa or pb is greater then 0, additionally OR<27>; R<27> = H or a protective group PG<6>; R<5> = H or 1-10C alkyl, 6-12C aryl, 7-20C aralkyl (all optionally substituted) or (CH2)s-T; s = 1-4; T = OR<22> or hal; R<22> = H or a protective group PG<4>; R<6>, R<7> = H or R<6> + R<7> = an additional bond or O; G = X=CR<8> or bi- or tri-cyclic aryl; R<8> = H, hal, CN or 1-20C alkyl, 6-12C aryl, 7-20C aralkyl (all optionally substituted); X = O, 2 OR<23> groups, 2-10C alkylene- alpha ,omega-dioxy, H/OR<9> or CR<10>R<11>; R<23> = 1-20C alkyl; R<9> = H or protective group PGx; R<10>, R<11> = H or 1-20C alkyl, 6-12C aryl or 7-20C aralkyl (all optionally substituted) or CR<10>R<11> = 5-7 membered carbocyclyl; D-E = CH2-CH2 or O-CH2; A-Y = OCO, O-CH2, CH2CO, NR<29>CO or NR<29>-SO2; R<29> = H or 1-10C alkyl; Z = O or H/OR<12>; R<12> = H or protective group PGz and hal = halogen. An Independent claim is included for the preparation of (I).

Description

Von Höfle et al. wird die cytotoxische Wirkung der Naturstoffe Epothilon A (R = Wasserstoff) und Epothilon B (R = Methyl)
By Höfle et al. the cytotoxic effects of the natural substances epothilone A (R = hydrogen) and epothilone B (R = methyl)

z. B. in Angew. Chem. 1996, 108, 1671-1673, beschrieben. Wegen der in-vitro- Selektivität gegenüber Brust- und Darmzelllinien und ihrer im Vergleich zu Taxol deutlich höheren Aktivität gegen P-Glycoprotein-bildende, multiresistente Tumorlinien sowie ihre gegenüber Taxol verbesserten physikalischen Eigenschaften, z. B. eine um den Faktor 30 höhere Wasserlöslichkeit, ist diese neuartige Strukturklasse für die Entwicklung eines Arzneimittels zur Therapie maligner Tumoren besonders interessant.e.g. B. in Angew. Chem. 1996, 108, 1671-1673. Because of the in vitro Selectivity to breast and colon cell lines and their compared to taxol significantly higher activity against P-glycoprotein-forming, multi-resistant Tumor lines as well as their physical improved compared to taxol Properties, e.g. B. a water solubility higher by a factor of 30 is this Novel structural class for the development of a drug for therapy malignant tumors particularly interesting.

Die Naturstoffe sind sowohl chemisch als auch metabolisch für eine Arzneimittelentwicklung nicht ausreichend stabil. Zur Beseitigung dieser Nachteile sind Modifikationen an dem Naturstoff nötig. Derartige Modifikationen sind nur auf totalsynthetischem Wege möglich und setzen Synthesestrategien voraus, die eine breite Modifikation des Naturstoffes ermöglichen. Ziel der Strukturveränderungen ist es auch, die therapeutische Breite zu erhöhen. Dies kann durch eine Verbesserung der Selektivität der Wirkung und/oder eine Erhöhung der Wirkstärke und/oder eine Reduktion unerwünschter toxischer Nebenwirkungen, wie sie in Proc. Natl. Acad. Sci. USA 1998, 95, 9642-9647 beschrieben sind, erfolgen.The natural products are both chemical and metabolic for one Drug development not sufficiently stable. To eliminate this Disadvantages are modifications to the natural product. Such modifications are only possible in a totally synthetic way and set synthesis strategies ahead, which allow a wide modification of the natural product. goal of Structural changes also increase the therapeutic breadth. This can be achieved by improving the selectivity of the effect and / or Increasing potency and / or reducing unwanted toxic Side effects as described in Proc. Natl. Acad. Sci. USA 1998, 95, 9642-9647 are described.

Die Totalsynthese von Epothilon A ist von Schinzer et al. in Chem. Eur. J. 1996, 2, No. 11, 1477-1482 und in Angew. Chem. 1997, 109, Nr. 5, S. 543-544 beschrieben. The total synthesis of epothilone A is by Schinzer et al. in Chem. Eur. J. 1996, 2, No. 11, 1477-1482 and in Angew. Chem. 1997, 109, No. 5, pp. 543-544 described.  

Epothilon-Derivate wurden bereits von Höfle et al. in der WO 97/19086 beschrieben. Diese Derivate wurden ausgehend vom natürlichen Epothilon A oder B hergestellt.Epothilone derivatives have already been described by Höfle et al. in WO 97/19086 described. These derivatives were based on the natural epothilone A or B.

Eine weitere Synthese von Epothilon und Epothilonderivaten wurde von Nicolaou et al. in Angew. Chem. 1997, 109, Nr. 1/2, S. 170-172 beschrieben. Die Synthese von Epothilon A und B und einiger Epothilon-Analoga wurde in Nature, Vol. 387, 1997, S. 268-272, die Synthese von Epothilon A und seinen Derivaten in J. Am. Chem. Soc., Vol. 119, No. 34, 1997, S. 7960-7973 sowie die Synthese von Epothilon A und B und einiger Epothilon-Analoga in J. Am. Chem. Soc., Vol. 119, No. 34, 1997, S. 7974-7991 ebenfalls von Nicolaou et al. beschrieben.Another synthesis of epothilone and epothilone derivatives was by Nicolaou et al. in Angew. Chem. 1997, 109, No. 1/2, pp. 170-172. The synthesis of epothilones A and B and some epothilone analogues has been described in Nature, Vol. 387, 1997, pp. 268-272, the synthesis of epothilone A and its Derivatives in J. Am. Chem. Soc., Vol. 119, No. 34, 1997, pp. 7960-7973 and the synthesis of epothilones A and B and some epothilone analogues in J. Am. Chem. Soc., Vol. 119, No. 34, 1997, pp. 7974-7991 also by Nicolaou et al. described.

Ebenfalls Nicolaou et al. beschreiben in Angew. Chem. 1997, 109, Nr. 19, S. 2181-2187 die Herstellung von Epothilon A-Analoga mittels kombinatorischer Festphasensynthese. Auch einige Epothilon B-Analoga sind dort beschrieben.Nicolaou et al. describe in Angew. Chem. 1997, 109, No. 19, p. 2181-2187 the production of epothilone A analogues by means of combinatorial Solid phase synthesis. Some epothilone B analogues are also described there.

Die Aufgabe der vorliegenden Erfindung besteht darin, neue Epothilon-Derivate zur Verfügung zu stellen, die sowohl chemisch als auch metabolisch für eine Arzneimittelentwicklung ausreichend stabil sänd und die hinsichtlich ihrer therapeutischen Breite, ihrer Selektivität der Wirkung und/oder unerwünschter toxischer Nebenwirkungen und/oder ihrer Wirkstärke den natürlichen Derivaten überlegen sind.The object of the present invention is to provide new epothilone derivatives to provide both chemically and metabolically for a Drug development is sufficiently stable and that in terms of its therapeutic breadth, their selectivity of action and / or undesirable toxic side effects and / or their potency of natural derivatives are superior.

Die vorliegende Erfindung beschreibt die neuen Epothilon-Derivate der allgemeinen Formel I,
The present invention describes the new epothilone derivatives of the general formula I

worin
R1a, R1b gleich oder verschieden sind und Wasserstoff, C1-C10-Alkyl, Aryl, C7-C20-Aralkyl, oder gemeinsam eine -(CH2)m-Gruppe mit m = 1, 2, 3, 4 oder 5, eine -(CH2)-O-(CH2)-Gruppe,
R2a Wasserstoff, C1-C10-Alkyl, Aryl, C7-C20-Aralkyl, -(CH2)ra-C∼C-(CH2)pa- R26a, -(CH2)ra-C=C-(CH2)pa-R26a
wherein
R 1a , R 1b are identical or different and are hydrogen, C 1 -C 10 alkyl, aryl, C 7 -C 20 aralkyl, or together a - (CH 2 ) m group with m = 1, 2, 3, 4 or 5, a - (CH 2 ) -O- (CH 2 ) group,
R 2a is hydrogen, C 1 -C 10 alkyl, aryl, C 7 -C 20 aralkyl, - (CH 2 ) ra -C∼C- (CH 2 ) pa - R 26a , - (CH 2 ) ra -C = C- (CH 2 ) pa -R 26a

R2b -(CH2)rb-C∼C-(CH2)pb-R26b, -(CH2)rb-C=C-(CH2)pb-R26b,
R 2b - (CH 2 ) rb -C∼C- (CH 2 ) pb -R 26b , - (CH 2 ) rb -C = C- (CH 2 ) pb -R 26b ,

ra, rb gleich oder verschieden sind und 0 bis 4,
pa, pb gleich oder verschieden sind und 0 bis 3,
n 0 bis 5,
R3a Wasserstoff, C1-C10-Alkyl, Aryl, C7-C20-Aralkyl,
R14 Wasserstoff, OR14a, Hal,
R3b OPG14,
R4 Wasserstoff, C1-C10-Alkyl, Aryl, C7-C20-Aralkyl, Hal, OR25, CN,
R25 Wasserstoff, eine Schutzgruppe PG5,
R26a, R26b gleich oder verschieden sind und Wasserstoff, C1-C10-Alkyl, Aryl, C7-C20-Aralkyl, C1-C10-Acyl, oder, falls pa bzw. pb <0 sind, eine Gruppe OR27,
R27 Wasserstoff, eine Schutzgruppe PG6,
R5 Wasserstoff, C1-C10-Alkyl, Aryl, C7-C20-Aralkyl, (CH2)s-A,
wobei s für 1, 2, 3 oder 4,
A für OR22 oder Hal,
R22 für Wasserstoff oder PG4 stehen,
R6, R7 je ein Wasserstoffatom, gemeinsam eine zusätzliche Bindung oder ein Sauerstoffatom,
R8 Wasserstoff, Halogen, CN, C1-C20-Alkyl, Aryl, C7-C20-Aralkyl, die alle substituiert sein können,
X ein Sauerstoffatom, zwei Alkoxygruppen OR23, eine C2-C10-Alkylen-α,ω- dioxygruppe, die geradkettig oder verzweigt sein kann, H/OR9 oder eine Gruppierung CR10R11,
wobei
R23 für einen C1-C20-Alkylrest,
R9 für Wasserstoff oder eine Schutzgruppe PGx,
R10, R11 gleich oder verschieden sind und für Wasserstoff, einen C1-C20- Alkyl-, Aryl-, C7-C20-Aralkylrest oder R10 und R11 zusammen mit dem Methylenkohlenstoffatom gemeinsam für einen 5- bis 7- gliedrigen carbocyclischen Ring stehen,
Y ein Sauerstoffatom oder zwei Wasserstoffatome,
Z ein Sauerstoffatom oder H/OR12,
wobei
R12 Wasserstoff oder eine Schutzgruppe PGz ist,
Hal Halogen, vorzugsweise Fluor, Chlor, Brom oder Iod, bedeuten.ra, rb are the same or different and 0 to 4,
pa, pb are the same or different and 0 to 3,
n 0 to 5,
R 3a is hydrogen, C 1 -C 10 alkyl, aryl, C 7 -C 20 aralkyl,
R 14 is hydrogen, OR 14a , Hal,
R 3b OPG 14 ,
R 4 is hydrogen, C 1 -C 10 alkyl, aryl, C 7 -C 20 aralkyl, Hal, OR 25 , CN,
R 25 is hydrogen, a protective group PG 5 ,
R 26a , R 26b are the same or different and are hydrogen, C 1 -C 10 alkyl, aryl, C 7 -C 20 aralkyl, C 1 -C 10 acyl, or, if pa or pb <0, one Group OR 27 ,
R 27 is hydrogen, a protective group PG 6 ,
R 5 is hydrogen, C 1 -C 10 alkyl, aryl, C 7 -C 20 aralkyl, (CH 2 ) s -A,
where s is 1, 2, 3 or 4,
A for OR 22 or Hal,
R 22 represents hydrogen or PG 4 ,
R 6 , R 7 each represent a hydrogen atom, together an additional bond or an oxygen atom,
R 8 is hydrogen, halogen, CN, C 1 -C 20 alkyl, aryl, C 7 -C 20 aralkyl, all of which can be substituted,
X is an oxygen atom, two alkoxy groups OR 23 , a C 2 -C 10 alkylene-α, ω- dioxy group, which can be straight-chain or branched, H / OR 9 or a group CR 10 R 11 ,
in which
R 23 represents a C 1 -C 20 alkyl radical,
R 9 represents hydrogen or a protective group PG x ,
R 10 , R 11 are the same or different and are hydrogen, a C 1 -C 20 alkyl, aryl, C 7 -C 20 aralkyl radical or R 10 and R 11 together with the methylene carbon atom together for a 5 to 7 - membered carbocyclic ring,
Y is an oxygen atom or two hydrogen atoms,
Z is an oxygen atom or H / OR 12 ,
in which
R 12 is hydrogen or a protective group PG z ,
Hal is halogen, preferably fluorine, chlorine, bromine or iodine.

Die Darstellung der neuen Epothilon-Derivate basiert auf der Verknüpfung dreier Teilfragmente A, B und C. Die Schnittstellen liegen wie in der allgemeinen Formel I' angedeutet.
The representation of the new epothilone derivatives is based on the linkage of three partial fragments A, B and C. The interfaces lie as indicated in the general formula I '.

A bedeutet ein C1-C6-Fragment (Epothilon-Zählweise) der allgemeinen Formel
A represents a C 1 -C 6 fragment (epothilone counting) of the general formula

worin
R1a', R1b', R2a' und R2b' die bereits für R1a, R1b, R2a und R2b genannten Bedeutungen haben und
R13 CH2OR13a, CH2-Hal, CHO, CO2R13b, COHal,
R14 Wasserstoff, OR14a, Hal, OSO2R14b,
R13a, R14a Wasserstoff, SO2-Alkyl, SO2-Aryl, SO2-Aralkyl oder gemeinsam eine -(CH2)o-Gruppe oder gemeinsam eine CR15aR15b-Gruppe,
R13b, R14b Wasserstoff, C1-C20-Alkyl, Aryl, C1-C20-Aralkyl,
R15a, R15b gleich oder verschieden sind und Wasserstoff, C1-C10-Alkyl, Aryl, C7-C20-Aralkyl, oder gemeinsam eine -(CH2)q-Gruppe,
o 2 bis 4,
q 3 bis 6,
einschließlich aller Stereoisomeren sowie deren Gemische bedeuten sowie
freie Hydroxylgruppen in R13 und R14 verethert oder verestert, freie Carbonylgruppen in A und R13 ketalisiert, in einen Enolether überführt oder reduziert sowie freie Säuregruppen in A in deren Salze mit Basen überführt sein können. wherein
R 1a ' , R 1b' , R 2a ' and R 2b' have the meanings already mentioned for R 1a , R 1b , R 2a and R 2b and
R 13 CH 2 OR 13a , CH 2 -Hal, CHO, CO 2 R 13b , COHal,
R 14 hydrogen, OR 14a , Hal, OSO 2 R 14b ,
R 13a , R 14a are hydrogen, SO 2 alkyl, SO 2 aryl, SO 2 aralkyl or together a - (CH 2 ) o group or together a CR 15a R 15b group,
R 13b , R 14b are hydrogen, C 1 -C 20 alkyl, aryl, C 1 -C 20 aralkyl,
R 15a , R 15b are identical or different and are hydrogen, C 1 -C 10 alkyl, aryl, C 7 -C 20 aralkyl, or together a - (CH 2 ) q group,
o 2 to 4,
q 3 to 6,
including all stereoisomers and their mixtures mean as well
free hydroxyl groups in R 13 and R 14 are etherified or esterified, free carbonyl groups in A and R 13 are ketalized, converted into an enol ether or reduced, and free acid groups in A can be converted into bases in their salts.

B steht für ein C7-C12-Fragment (Epothilon-Zählweise) der allgemeinen Formel
B stands for a C 7 -C 12 fragment (epothilone counting) of the general formula

worin
R3a', R4' und R5' die bereits für R3a, R4 und R5 genannten Bedeutungen haben, und
V ein Sauerstoffatom, zwei Alkoxygruppen OR17, eine C2-C10-Alkylen-α,ω- dioxygruppe, die geradkettig oder verzweigt sein kann oder H/OR16,
W ein Sauerstoffatom, zwei Alkoxygruppen OR19, eine C2-C10-Alkylen-α,ω- dioxygruppe, die geradkettig oder verzweigt sein kann oder H/OR18,
R16, R18 unabhängig voneinander Wasserstoff oder eine Schutzgruppe PG1,
R17, R19 unabhängig voneinander C1-C20-Alkyl, bedeuten.wherein
R 3a ' , R 4' and R 5 'have the meanings already given for R 3a , R 4 and R 5 , and
V is an oxygen atom, two alkoxy groups OR 17 , a C 2 -C 10 alkylene-α, ω- dioxy group, which can be straight-chain or branched, or H / OR 16 ,
W is an oxygen atom, two alkoxy groups OR 19 , a C 2 -C 10 -alkylene-α, ω- dioxy group, which can be straight-chain or branched, or H / OR 18 ,
R 16 , R 18 independently of one another are hydrogen or a protective group PG 1 ,
R 17 , R 19 independently of one another are C 1 -C 20 alkyl.

C steht für ein C13-C16-Fragment (Epothilon-Zählweise) der allgemeinen Formel
C stands for a C 13 -C 16 fragment (epothilone counting) of the general formula

worin
R8' die bereits in der allgemeinen Formel I für R8 genannte Bedeutung hat und
R7' ein Wasserstoffatom,
R20 ein Wasserstoffatom oder eine Schutzgruppe PG2,
R21 eine Hydroxygruppe, Halogen, eine geschützte Hydroxygruppe OPG3, ein Phosphoniumhalogenidrest PPh3 +Hal- (Ph = Phenyl; Hal = F, Cl, Br, I), ein Phosphonatrest P(O)(OQ)2 (Q = C1-C10-Alkyl oder Phenyl) oder ein Phosphinoxidrest P(O)Ph2 (Ph = Phenyl),
U ein Sauerstoffatom, zwei Alkoxygruppen OR23, eine C2-C10-Alkylen-α,ω- dioxygruppe, die geradkettig oder verzweigt sein kann, H/OR9 oder eine Gruppierung CR10R11,
wobei
R23 für einen C1-C20-Alkylrest,
R9 für Wasserstoff oder eine Schutzgruppe PG3,
R10, R11 gleich oder verschieden sind und für Wasserstoff, einen C1-C20- Alkyl-, Aryl-, C7-C20-Aralkylrest oder R10 und R11 zusammen mit dem Methylenkohlenstoffatom gemeinsam für einen 5- bis 7-gliedrigen carbocyclischen Ring stehen,
bedeuten.wherein
R 8 'has the meaning already given for R 8 in the general formula I and
R 7 'is a hydrogen atom,
R 20 is a hydrogen atom or a protective group PG 2 ,
R 21 is a hydroxy group, halogen, a protected hydroxy group OPG 3 , a phosphonium halide residue PPh 3 + Hal - (Ph = phenyl; Hal = F, Cl, Br, I), a phosphonate residue P (O) (OQ) 2 (Q = C 1 -C 10 alkyl or phenyl) or a phosphine oxide residue P (O) Ph 2 (Ph = phenyl),
U is an oxygen atom, two alkoxy groups OR 23 , a C 2 -C 10 alkylene-α, ω- dioxy group, which can be straight-chain or branched, H / OR 9 or a group CR 10 R 11 ,
in which
R 23 represents a C 1 -C 20 alkyl radical,
R 9 represents hydrogen or a protective group PG 3 ,
R 10 , R 11 are the same or different and are hydrogen, a C 1 -C 20 alkyl, aryl, C 7 -C 20 aralkyl radical or R 10 and R 11 together with the methylene carbon atom together for a 5 to 7 -linked carbocyclic ring,
mean.

Als Alkylgruppen R1a, R1b, R2a, R3a, R4, R5, R8, R10, R11, R13b, R14b, R15a, R15b, R17, R19, R23, R24, R26a, R26b und R28 sind gerad- oder verzweigtkettige Alkylgruppen mit 1-20 Kohlenstoffatomen zu betrachten, wie beispielsweise Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, tert.-Butyl, Pentyl, Isopentyl, Neopentyl, Heptyl, Hexyl, Decyl.As alkyl groups R 1a , R 1b , R 2a , R 3a , R 4 , R 5 , R 8 , R 10 , R 11 , R 13b , R 14b , R 15a , R 15b , R 17 , R 19 , R 23 , R 24 , R 26a , R 26b and R 28 are straight or branched chain alkyl groups with 1-20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, Heptyl, hexyl, decyl.

Die Alkylgruppen R1a, R1b, R2a, R3a, R4, R5, R8, R10, R11, R13b, R14b, R15a, R15b, R17, R19, R23, R24, R26a, R26b und R28 können perfluoriert oder substituiert sein durch 1-5 Halogenatome, Hydroxygruppen, C1-C4- Alkoxygruppen, C6-C12-Arylgruppen (die durch 1-3 Halogenatome substituiert sein können).The alkyl groups R 1a , R 1b , R 2a , R 3a , R 4 , R 5 , R 8 , R 10 , R 11 , R 13b , R 14b , R 15a , R 15b , R 17 , R 19 , R 23 , R 24 , R 26a , R 26b and R 28 can be perfluorinated or substituted by 1-5 halogen atoms, hydroxy groups, C 1 -C 4 alkoxy groups, C 6 -C 12 aryl groups (which can be substituted by 1-3 halogen atoms) .

Als Arylrest R1a, R1b, R2a, R3a, R4, R5, R8, R10, R11, R13b, R14b, R15a, R15b, R24, R26a, R26b und R28 kommen substituierte und unsubstituierte carbocyclische oder heterocyclische Reste mit einem oder mehreren Heteroatomen wie z. B. Phenyl, Naphthyl, Furyl, Thienyl, Pyridyl, Pyrazolyl, Pyrimidinyl, Oxazolyl, Pyridazinyl, Pyrazinyl, Chinolyl, Thiazolyl, die einfach oder mehrfach substituiert sein können durch Halogen, OH, O-Alkyl, CO2H, CO2- Alkyl, -NH2, -NO2, -N3, -CN, C1-C20-Alkyl, C1-C20-Acyl, C1-C20-Acyloxy- Gruppen, in Frage. As aryl radicals R 1a , R 1b , R 2a , R 3a , R 4 , R 5 , R 8 , R 10 , R 11 , R 13b , R 14b , R 15a , R 15b , R 24 , R 26a , R 26b and R 28 come substituted and unsubstituted carbocyclic or heterocyclic radicals with one or more heteroatoms such as. B. phenyl, naphthyl, furyl, thienyl, pyridyl, pyrazolyl, pyrimidinyl, oxazolyl, pyridazinyl, pyrazinyl, quinolyl, thiazolyl, which can be mono- or polysubstituted by halogen, OH, O-alkyl, CO 2 H, CO 2 - alkyl , -NH 2 , -NO 2 , -N 3 , -CN, C 1 -C 20 alkyl, C 1 -C 20 acyl, C 1 -C 20 acyloxy groups, in question.

Die Aralkylgruppen in R1a, R1b, R2a, R3a, R4, R5, R8, R10, R11, R13b, R14b, R15a, R15b, R24, R26a, R26b und R28 können im Ring bis 14 C-Atome, bevorzugt 6 bis 10 und in der Alkylkette 1 bis 8, bevorzugt 1 bis 4 Atome enthalten. Als Aralkylreste kommen beispielweise in Betracht Benzyl, Phenylethyl, Naphthylmethyl, Naphthylethyl, Furylmethyl, Thienylethyl, Pyridylpropyl. Die Ringe können einfach oder mehrfach substituiert sein durch Halogen, OH, O-Alkyl, CO2H, CO2-Alkyl, -NO2, -N3, -CN, C1-C20-Alkyl, C1-C20- Acyl, C1-C20-Acyloxy-Gruppen.The aralkyl groups in R 1a , R 1b , R 2a , R 3a , R 4 , R 5 , R 8 , R 10 , R 11 , R 13b , R 14b , R 15a , R 15b , R 24 , R 26a , R 26b and R 28 can contain up to 14 carbon atoms, preferably 6 to 10, in the ring and 1 to 8, preferably 1 to 4, atoms in the alkyl chain. Examples of suitable aralkyl radicals are benzyl, phenylethyl, naphthylmethyl, naphthylethyl, furylmethyl, thienylethyl, pyridylpropyl. The rings can be mono- or polysubstituted by halogen, OH, O-alkyl, CO 2 H, CO 2 alkyl, -NO 2 , -N 3 , -CN, C 1 -C 20 alkyl, C 1 -C 20 - Acyl, C 1 -C 20 acyloxy groups.

Die in X in der allgemeinen Formel I enthaltenen Alkoxygruppen sollen jeweils 1 bis 20 Kohlenstoffatome enthalten, wobei Methoxy-, Ethoxy- Propoxy-, Isopropoxy- und t-Butyloxygruppen bevorzugt sind.The alkoxy groups contained in X in general formula I are each intended to be 1 contain up to 20 carbon atoms, methoxy, ethoxy propoxy, Isopropoxy and t-butyloxy groups are preferred.

Als Vertreter für die Schutzgruppen PG sind Alkyl- und/oder Aryl-substituiertes Silyl, C1-C20-Alkyl, C4-C7-Cycloalkyl, das im Ring zusätzlich ein Sauerstoffatom enthalten kann, Aryl, C7-C20-Aralkyl, C1-C20-Acyl sowie Aroyl zu nennen.Representatives for the protective groups PG are alkyl- and / or aryl-substituted silyl, C 1 -C 20 alkyl, C 4 -C 7 cycloalkyl, which may additionally contain an oxygen atom in the ring, aryl, C 7 -C 20 - Aralkyl, C 1 -C 20 acyl and aroyl to name.

Als Alkyl-, Silyl- und Acylreste für die Schutzgruppen PG kommen die dem Fachmann bekannten Reste in Betracht. Bevorzugt sind aus den entsprechenden Alkyl- und Silylethern leicht abspaltbare Alkyl- bzw. Silylreste, wie beispielsweise der Methoxymethyl-, Methoxyethyl-, Ethoxyethyl-, Tetrahydropyranyl-, Tetrahydrofuranyl-, Trimethylsilyl-, Triethylsilyl-, tert.- Butyldimethylsilyl-, tert.-Butyldiphenylsilyl-, Tribenzylsilyl-, Triisopropylsilyl-, Benzyl-, para-Nitrobenzyl-, para-Methoxybenzyl-Rest sowie Alkylsulfonyl- und Arylsulfonylreste. Als Acylreste kommen z. B. Formyl, Acetyl, Propionyl, Isopropionyl, Pivalyl-, Butyryl oder Benzoyl, die mit Amino- und/oder Hydroxygruppen substituiert sein können, in Frage.The alkyl, silyl and acyl radicals for the protective groups PG come from Residues known to those skilled in the art. Preferred from the corresponding alkyl and silyl ethers easily removable alkyl or silyl radicals, such as the methoxymethyl, methoxyethyl, ethoxyethyl, Tetrahydropyranyl, tetrahydrofuranyl, trimethylsilyl, triethylsilyl, tert.- Butyldimethylsilyl-, tert-butyldiphenylsilyl-, tribenzylsilyl-, triisopropylsilyl-, Benzyl, para-nitrobenzyl, para-methoxybenzyl radical and alkylsulfonyl and Arylsulfonyl residues. As acyl residues come e.g. B. formyl, acetyl, propionyl, Isopropionyl, pivalyl, butyryl or benzoyl, with amino and / or Hydroxy groups can be substituted, in question.

Die Acylgruppen PGx bzw. PGz in R9, R12, R26a und R26b können 1 bis 20 Kohlenstoffatome enthalten, wobei Formyl-, Acetyl-, Propionyl-, Isopropionyl und Pivalylgruppen bevorzugt sind.The acyl groups PG x and PG z in R 9 , R 12 , R 26a and R 26b can contain 1 to 20 carbon atoms, formyl, acetyl, propionyl, isopropionyl and pivalyl groups being preferred.

Der Index m in der aus R1a und R1b gebildeten Alkylengruppe steht vorzugsweise für 1, 2, 3 oder 4.The index m in the alkylene group formed from R 1a and R 1b is preferably 1, 2, 3 or 4.

Die für V, W und X mögliche C2-C10-Alkylen-α,ω-dioxygruppe ist vorzugsweise eine Ethylenketal- oder Neopentylketalgruppe. The C 2 -C 10 alkylene-α, ω-dioxy group which is possible for V, W and X is preferably an ethylene ketal or neopentyl ketal group.

Die nachstehend genannten Verbindungen sind erfindungsgemäß bevorzugt:
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- fluor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-pyridyl)ethenyl)- 1-oxa-5,5-trimethylen-9,13-dimethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-pyridyl)ethenyl)-1-oxa- 5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(2-(2- pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9- dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-13-ethyl-16-(1-methyl-2-(2- pyridyl)ethenyl)-1-oxa-5,5,9-trimethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-16-ethyl-10-(but-3-in-1-yl)- 3-(1-methyl-2-(2-pyridyl)ethenyl)-8,8,12-trimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-pyridyl)ethenyl)-1-oxa- 5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(2-(2- pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9- dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- fluor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- chlor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-pyridyl)ethenyl)-1-oxa- 5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(2-(2- pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9- dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- fluor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- chlor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2- pyridyl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-pyridyl)ethenyl)-1-oxa- 5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2- pyridyl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-fluor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2- pyridyl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-chlor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-pyridyl)ethenyl)-1-oxa- 5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(2- (2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan- 5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- fluor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- chlor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-pyridyl)ethenyl)-1-oxa- 5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(2- (2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan- 5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- fluor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- chlor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2- pyridyl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl- 4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-pyridyl)ethenyl)-1-oxa- 5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2- pyridyl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-fluor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl- 4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2- pyridyl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-chlor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl- 4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methylthiazol-4-yl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclahexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(2-(2- methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- chlor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methylthiazol-4-yl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(2-(2- methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- chlor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2- methylthiazol-4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1- ethyl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol- 4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methylthiazol- 4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-chlor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methylthiazol-4-yl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(2- (2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- chlor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methylthiazol-4-yl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(2- (2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- chlor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2- methylthiazol-4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16- tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)-cyclohexadec- 13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16- tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol- 4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16- tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methylthiazol- 4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-chlor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16- tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- methyl-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methyloxazol-4-yl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(2-(2- methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- fluor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- chlor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- methyl-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methyloxazol-4-yl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(2-(2- methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- fluor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- chlor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2- methyloxazol-4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1- ethyl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-methyl-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methyloxazol- 4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-fluor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methyloxazol- 4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-chlor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- methyl-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methyloxazol-4-yl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(2- (2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- fluor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13 E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- chlor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- methyl-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methyloxazol-4-yl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(2- (2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- fluor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,165(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- chlor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2- methyloxazol-4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-methyl-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16- tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)-cyclohexadec- 13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS), 11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16- tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methyloxazol- 4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-fluor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16- tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methyloxazol- 4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-chlor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16- tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)- 1-oxa-5,5-trimethylen-9,13-d imethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-pyridyl)ethenyl)-1- oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- fluor-2-(2-pyridyl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-pyridyl)ethenyl)-1- oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- fluor-2-(2-pyridyl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2- pyridyl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-fluor-2-(2-pyridyl)ethenyl)-8,8-trimethylen-12,16- dimethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-in-1-yl)-cyclohexadec- 13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-in-1-yl)-cyclohexadec- 13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-methylthiazol-4-yl)ethenyl)- 1-oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(2- (2-methylthiazol-4-yl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol- 4-yl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8- trimethylen-12,16-dimethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methyloxazol-4-yl)ethenyl)- 1-oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(2- (2-methyloxazol-4-yl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-in-1-yl)-cyclohexadec- 13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- fluor-2-(2-methyloxazol-4-yl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-en-1-yl)-cyclohexadec- 13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- methyl-2-(2-methyloxazol-4-yl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-en-1-yl)-cyclohexadec- 13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- fluor-2-(2-methyloxazol-4-yl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(2-(2-methyloxazol-4-yl)ethenyl)-8,8-trimethylen- 12,16-dimethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methyloxazol- 4-yl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-chlor-2-(2-methyloxazol-4-yl)ethenyl)-8,8- trimethylen-12,16-dimethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion. The compounds mentioned below are preferred according to the invention:
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-methyl- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-methyl- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1-methyl- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-fluoro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-fluoro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2-pyridyl) ethenyl) - 1-oxa-5,5-trimethylene-9 , 13-dimethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-methyl- 2- (2-pyridyl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (2- (2-pyridyl) ethenyl) -1-oxa- 5,5,9,13- tetramethyl-7- (but-3-in-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (2- (2nd - pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-13-ethyl-16- (1-methyl-2- (2-pyridyl) ethenyl) -1-oxa- 5,5,9-trimethyl-7- (but-3-in-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-16-ethyl-10- (but-3-in-1-yl) - 3- ( 1-methyl-2- (2-pyridyl) ethenyl) -8,8,12-trimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-methyl- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (2- (2-pyridyl) ethenyl) -1-oxa- 5,5,9,13- tetramethyl-7- (but-3-in-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (2- (2nd - pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-fluoro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1- chloro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1-methyl- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (2- (2-pyridyl) ethenyl) -1-oxa- 5,5,9,13- tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (2- (2nd - pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1- fluoro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1- chloro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-methyl -2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-pyridyl) ethenyl) -1-oxa- 5,5,9 , 13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (2- ( 2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-fluor -2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-pyridyl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-chloro -2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1-methyl- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (2- (2-pyridyl) ethenyl) -1-oxa- 5,5,9,13- tetramethyl-7- (prop-2-in-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (2- (2nd -pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- fluoro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- chloro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1-methyl- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (2- (2-pyridyl) ethenyl) -1-oxa- 5,5,9,13- tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (2- (2nd -pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- fluoro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- chloro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-methyl-2- (2- pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-pyridyl) ethenyl) -1-oxa- 5,5,9 , 13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-fluoro-2- (2- pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-pyridyl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-chloro-2- (2- pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-methyl- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methylthiazol-4-yl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (but-3-yn-1-yl) cyclahexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (2- (2nd - methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-fluoro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1- chloro-2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1-methyl- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methylthiazol-4-yl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (2- (2nd - methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1- fluoro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1- chloro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-methyl-2- (2-methylthiazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-methyl -2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methylthiazol-4-yl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (2- ( 2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-fluor -2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methylthiazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-chloro -2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1-methyl- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methylthiazol-4-yl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (2- (2nd -methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- fluoro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- chloro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1-methyl- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methylthiazol-4-yl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (2- (2nd -methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- fluoro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- chloro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-methyl-2- (2-methylthiazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-methyl-2- (2- methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methylthiazol-4-yl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (2- (2-methylthiazole-4- yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-fluoro-2- (2- methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methylthiazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-chloro-2- (2- methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-methyl- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methyloxazol-4-yl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (2- (2nd - methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-fluoro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1- chloro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1-methyl- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methyloxazol-4-yl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (2- (2nd - methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1- fluoro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1- chloro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-methyl-2- (2-methyloxazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-methyl -2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methyloxazol-4-yl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (2- ( 2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methyloxazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-fluor -2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methyloxazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-chloro -2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1-methyl- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methyloxazol-4-yl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (2- (2nd -methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- fluoro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13 E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa -5,5,9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- chloro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1-methyl- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methyloxazol-4-yl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (2- (2nd -methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- fluoro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 165 (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- chloro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-methyl-2- (2-methyloxazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-methyl-2- (2- methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methyloxazol-4-yl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (2- (2-methyloxazole-4- yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methyloxazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-fluoro-2- (2- methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methyloxazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-chloro-2- (2- methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) - 1-oxa-5,5- trimethylene-9,13-d imethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-methyl- 2- (2-pyridyl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5,5- trimethylene-9,13-dimethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- fluoro- 2- (2-pyridyl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5,5- trimethylene-9,13-dimethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- fluoro- 2- (2-pyridyl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5 , 5-trimethylene-9,13-dimethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-fluoro-2- (2- pyridyl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5-trimethylene-9,13-dimethyl-7- (prop-2-in-1-yl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1-methyl- 2- (2-methylthiazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5-trimethylene-9,13-dimethyl-7- (prop-2-in-1-yl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- fluoro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2-methylthiazol-4-yl) ethenyl) - 1-oxa-5,5-trimethylene-9 , 13-dimethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (2- (2nd -methylthiazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1 -oxa-5,5-trimethylene-9,13-dimethyl-7- (oxacyclopropylmethyl) - cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-fluoro-2- (2- methylthiazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methyloxazol-4-yl) ethenyl) - 1-oxa-5,5- trimethylene-9,13-dimethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (2- (2nd -methyloxazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5-trimethylene-9,13-dimethyl-7- (prop-2-in-1-yl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- fluoro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5-trimethylene-9,13-dimethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1-methyl- 2- (2-methyloxazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5-trimethylene-9,13-dimethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- fluoro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methyloxazol-4-yl) ethenyl) -1-oxa-5 , 5-trimethylene-9,13-dimethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (2- (2-methyloxazole-4- yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methyloxazol-4-yl) ethenyl) -1 -oxa-5,5-trimethylene-9,13-dimethyl-7- (oxacyclopropylmethyl) - cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-chloro-2- (2- methyloxazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione.

Darstellung der Teilfragmente ARepresentation of the partial fragments A

Die Teilfragmente (Synthesebausteine) der allgemeinen Formel A lassen sich ausgehend von den in WO 99/07692 beschriebenen Vorstufen wie beispielsweise A-I herstellen. Dies wird beispielhaft in Schema 1 weiter ausgeführt.The partial fragments (synthesis building blocks) of the general formula A can be starting from the precursors described in WO 99/07692, such as for example, make A-I. This is further exemplified in Scheme 1 executed.

Schema 1 Scheme 1

Schritt a (A-I ⇒ A-II)Step a (A-I ⇒ A-II)

Die durch PG7 in A-I geschützte Hydroxylgruppe wird freigesetzt. Als Schutzgruppe PG7 kommen die, dem Fachmann bekannten Schutzgruppen wie z. B. der Methoxymethyl-, Methoxyethyl-, Ethoxyethyl-, Tetrahydropyranyl-, Tetrahydrofuranyl-, Trimethylsilyl-, Triethylsilyl-, tert.-Butyldimethylsilyl-, tert.- Butyldiphenylsilyl-, Tribenzylsilyl-, Triisopropylsilyl-, Benzyl-, para-Nitrobenzyl-, para-Methoxybenzyl-, Formyl-, Acetyl-, Propionyl-, Isopropionyl-, Pivalyl-, Butyryl- oder Benzoylrest in Frage.The hydroxyl group protected by PG 7 in AI is released. As protective group PG 7 come the protective groups known to the person skilled in the art, such as, for. B. the methoxymethyl, methoxyethyl, ethoxyethyl, tetrahydropyranyl, tetrahydrofuranyl, trimethylsilyl, triethylsilyl, tert.-butyldimethylsilyl, tert.-butyldiphenylsilyl, tribenzylsilyl, triisopropylsilyl, nitro para-methoxybenzyl, formyl, acetyl, propionyl, isopropionyl, pivalyl, butyryl or benzoyl in question.

Eine Übersicht befindet sich z. B. in "Protective Groups in Organic Synthesis" (Theodora W. Green, John Wiley and Sons). An overview is z. B. in "Protective Groups in Organic Synthesis" (Theodora W. Green, John Wiley and Sons).  

Bevorzugt sind solche Schutzgruppen, die unter Einwirkung von Fluorid gespalten werden können, wie z. B. der Trimethylsilyl-, tert.-Butyldimethylsilyl-, tert.-Butyldiphenylsilyl-, Tribenzylsilyl-, Triisopropylsilyl-Rest.Preference is given to those protective groups which are exposed to fluoride can be split, such as. B. the trimethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, tribenzylsilyl, triisopropylsilyl radical.

Besonders bevorzugt ist der tert.-Butyldimethylsilyl-, der Triisopropylsilyl- und der tert.-Butyldiphenylsilyl-Rest.The tert-butyldimethylsilyl, the triisopropylsilyl and the tert-butyldiphenylsilyl radical.

Als Schutzgruppen PG8a und PG8b kommen die bereits für PG7 genannten Gruppen sowie gemeinsam eine -CR28aR28b- -Gruppe, worin R28a und R28b gleich oder verschieden sein können und Wasserstoff, C1-C10-Alkyl, Aryl, C7-C20- Aralkyl bedeuten, in Frage.Protecting groups PG 8a and PG 8b include the groups already mentioned for PG 7 and together a —CR 28a R 28b - group, in which R 28a and R 28b can be the same or different and hydrogen, C 1 -C 10 alkyl, aryl , C 7 -C 20 aralkyl mean in question.

Bevorzugt sind solche -CR28aR28b- -Schutzgruppen, worin R28a und R28b C1-C8-Alkyl oder R28a Wasserstoff und R28b Aryl bedeuten.Preferred are -CR 28a R 28b - protective groups, in which R 28a and R 28b are C 1 -C 8 alkyl or R 28a is hydrogen and R 28b is aryl.

Besonders bevorzugt ist eine -C(CH3)2- -Gruppe.A -C (CH 3 ) 2 - group is particularly preferred.

Die Schutzgruppe PG7 wird nach den dem Fachmann bekannten Verfahren gespalten. Handelt es sich um einen Silylether, so eignet sich für die Spaltung die Umsetzung mit Fluoriden wie beispielsweise Tetrabutylammoniumfluorid, dem Fluorwasserstoff-Pyridin-Komplex, Kaliumfluorid oder die Anwendung verdünnter Mineralsäuren, die Verwendung von katalytischen Mengen Säuren wie z. B. para-Toluolsulfonsäure, para-Toluolsulfonsäure-pyridiniumsalz, Camphersulfonsäure in alkoholischen Lösungen, vorzugsweise in Ethanol oder Isopropanol.The protective group PG 7 is cleaved by the processes known to the person skilled in the art. If it is a silyl ether, the reaction with fluorides such as tetrabutylammonium fluoride, the hydrogen fluoride-pyridine complex, potassium fluoride or the use of dilute mineral acids, the use of catalytic amounts of acids such as e.g. B. para-toluenesulfonic acid, para-toluenesulfonic acid pyridinium salt, camphorsulfonic acid in alcoholic solutions, preferably in ethanol or isopropanol.

Schritt b (A-II ⇒ A-III)Step b (A-II ⇒ A-III)

Die Oxidation des primären Alkohols in A-II zum Aldehyd A-III erfolgt nach den, dem Fachmann bekannten Methoden. Beispielsweise genannt sei die Oxidation mit Pyridiniumchlorochromat, Pyridiniumdichromat, Chromtrioxid-Pyridin- Komplex, die Oxidation nach Swern oder verwandter Methoden z. B. unter Verwendung von Oxalylchlorid in Dimethylsulfoxid, die Verwendung des Dess- Martin-Periodinans, die Verwendung von Stickstoffoxiden wie z. B. N-Methyl- morpholino-N-oxid in Gegenwart geeigneter Katalysatoren wie z. B. Tetrapropylammoniumperruthenat in inerten Lösungsmitteln. Bevorzugt ist die Oxidation nach Swern sowie mit N-Methyl-morpholino-N-oxid unter Verwendung von Tetrapropylammoniumperruthenat. The oxidation of the primary alcohol in A-II to the aldehyde A-III takes place according to the methods known to the person skilled in the art. Oxidation is one example with pyridinium chlorochromate, pyridinium dichromate, chromium trioxide-pyridine Complex, the oxidation by Swern or related methods z. More colorful Use of oxalyl chloride in dimethyl sulfoxide, the use of the Dess Martin Periodinans, the use of nitrogen oxides such. B. N-methyl morpholino-N-oxide in the presence of suitable catalysts such. B. Tetrapropylammonium perruthenate in inert solvents. The is preferred Oxidation according to Swern and with N-methyl-morpholino-N-oxide using of tetrapropylammonium perruthenate.  

Schritt c (A-III ⇒ A-IV)Step c (A-III ⇒ A-IV)

Die Umsetzung der Aldehyde A-III zu Alkoholen der Formel A-IV erfolgt mit metallorganischen Verbindungen der theoretischen Formel M-CH2R2a', worin M für Indium, ein Alkalimetall, vorzugsweise Lithium oder ein zweiwertiges Metall MX, worin X ein Halogen repräsentiert und der Rest R2a' die oben genannten Bedeutungen aufweist. Als zweiwertiges Metall ist bevorzugt Magnesium und Zink, als Halogen X ist bevorzugt Chlor, Brom und Iod.The reaction of the aldehydes A-III to alcohols of the formula A-IV takes place with organometallic compounds of the theoretical formula M-CH 2 R 2a ' , where M is indium, an alkali metal, preferably lithium or a divalent metal MX, where X represents a halogen and the radical R 2a 'has the meanings given above. Magnesium and zinc are preferred as divalent metal, and chlorine, bromine and iodine are preferred as halogen X.

Schritt d (A-IV ⇒ A-V)Step d (A-IV ⇒ A-V)

Die Oxidation des sekundären Alkohols in A-IV zum Keton A-V erfolgt nach den, unter Schritt b) genannten Bedingungen. Bevorzugt ist die Oxidation mit N- Methyl-morpholino-N-oxid unter Verwendung von Tetrapropylammoniumperruthenat.The oxidation of the secondary alcohol in A-IV to ketone A-V takes place according to the conditions mentioned under step b). Oxidation with N- Methyl-morpholino-N-oxide using Tetrapropylammonium perruthenate.

Schritt e (A-V ⇒ A-VI)Step e (A-V ⇒ A-VI)

Zur optionalen Einführung eines Restes R2b', der außer Wasserstoff die bereits genannten Bedeutungen besitzen kann, wird das Keton der allgemeinen Formel A-V unter Verwendung starker Basen wie vorzugsweise Lithiumdiisopropylamid in das Enolat mit M in der Bedeutung des Gegenkations überführt.For the optional introduction of a radical R 2b 'which , apart from hydrogen, can have the meanings already mentioned, the ketone of the general formula AV is converted into the enolate with M in the meaning of the counter cation using strong bases, such as preferably lithium diisopropylamide.

Schritt f (A-VI ⇒ A-VII)Step f (A-VI ⇒ A-VII)

Das Enolat der Formel A-VI wird mit einer Verbindung der allgemeinen Formel X-R2b', worin X ein Halogen oder eine sonstige Abgangsguppe wie beispielsweise ein Alkyl- oder Arylsulfonat repräsentiert, umgesetzt. Als Halogen X ist bevorzugt Chlor, Brom und Iod.The enolate of the formula A-VI is reacted with a compound of the general formula XR 2b ' , in which X represents a halogen or another leaving group such as, for example, an alkyl or aryl sulfonate. The halogen X is preferably chlorine, bromine and iodine.

Darstellung der Teilfragmente BRepresentation of the partial fragments B

Die Teilfragmente (Synthesebausteine) der allgemeinen Formel B lassen sich wie in WO 99/07692 beschrieben herstellen.The partial fragments (synthesis building blocks) of the general formula B can be produce as described in WO 99/07692.

Darstellung der Teilfragmente CRepresentation of the partial fragments C

Die Teilfragmente (Synthesebausteine) der allgemeinen Formel C lassen sich wie in DE 197 51 200.3, DE 199 07 480.1 und WO 99/07692 beschrieben herstellen.The partial fragments (synthesis building blocks) of the general formula C can be as described in DE 197 51 200.3, DE 199 07 480.1 and WO 99/07692 produce.

Darstellung der Teilfragmente ABC und deren Zyklisierung zu I erfolgt ebenfalls analog wie in WO 99/07692 für zahlreiche Epothilon-Derivate beschrieben ist, mit der Abweichung, daß in den bekannten Derivaten in 6-Position kein ungesättigter Rest steht. WO 99/07692 belegt schon die allgemeine Anwendbarkeit des nachfolgend für die erfindungsgemäßen Verbindungen beschriebenen Syntheseprinzips. Außerdem gehen aus WO 99/07692 zahlreiche Synthesebausteine der allgemeinen Formeln A, B und C hervor, mit denen, gegebenenfalls in modifizierter Form im Falle der erfindungsgemäßen Substitution am Kohlenstoffatom 6, sich weitere der hier beanspruchten Verbindungen der allgemeinen Formel I erhalten lassen. Synthesebausteine der allgemeinen Formel C, in denen als R8 ein Halogenatom, insbesondere ein Fluoratom, vorhanden ist, sind Gegenstand der DE 199 07 480.1.Representation of the partial fragments ABC and their cyclization to I is also carried out analogously as described in WO 99/07692 for numerous epothilone derivatives, with the difference that there is no unsaturated residue in the known derivatives in the 6-position. WO 99/07692 already proves the general applicability of the synthetic principle described below for the compounds according to the invention. In addition, WO 99/07692 shows numerous synthesis building blocks of the general formulas A, B and C, with which, if appropriate in modified form in the case of the substitution at the carbon atom 6 according to the invention, further compounds of the general formula I claimed here can be obtained. Synthetic building blocks of the general formula C in which R 8 is a halogen atom, in particular a fluorine atom, are the subject of DE 199 07 480.1.

Teilfragmente der allgemeinen Formel AB
Partial fragments of the general formula AB

worin R1a', R1b', R2a', R2b', R3a, R4, R5, R13, R14, V und Z die bereits genannten Bedeutungen haben und PG14 ein Wasserstoffatom oder eine Schutzgruppe PG darstellt, werden aus den zuvor genannten Fragmenten A und B nach dem in Schema 2 gezeigten Verfahren erhalten. wherein R 1a ' , R 1b' , R 2a ' , R 2b' , R 3a , R 4 , R 5 , R 13 , R 14 , V and Z have the meanings already mentioned and PG 14 represents a hydrogen atom or a protective group PG , are obtained from the aforementioned fragments A and B by the method shown in Scheme 2.

Schema 2 Scheme 2

Schritt aa (A + B ⇒ AB)Step aa (A + B ⇒ AB)

Die Verbindung B, worin W die Bedeutung eines Sauerstoffatomes hat und eventuell vorhandene zusätzliche Carbonylgruppen geschützt sind, wird mit dem Enolat einer Carbonylverbindung der allgemeinen Formel A alkyliert. Das Enolat wird durch Einwirkung starker Basen wie z. B. Lithiumdiisopropylamid, Lithiumhexamethyldisilazan bei niedrigen Temperaturen hergestellt.The compound B, in which W has the meaning of an oxygen atom and any additional carbonyl groups that may be present are protected with the Alkylated enolate of a carbonyl compound of the general formula A. The enolate is by the action of strong bases such. B. lithium diisopropylamide, Lithium hexamethyldisilazane produced at low temperatures.

Teilfragmente der allgemeinen Formel BC
Partial fragments of the general formula BC

worin R3a, R4, R5, R6, R7, R8, U und W die bereits genannten Bedeutungen haben und PG12 ein Wasserstoffatom oder eine Schutzgruppe PG darstellt, werden aus den zuvor beschriebenen Fragmenten B und C nach dem in Schema 3 gezeigten Verfahren erhalten. wherein R 3a , R 4 , R 5 , R 6 , R 7 , R 8 , U and W have the meanings already mentioned and PG 12 represents a hydrogen atom or a protective group PG, from the fragments B and C described above according to the in Obtain the procedure shown in Scheme 3.

Schema 3 Scheme 3

Schritt ab (B + C ⇒ BC)Step from (B + C ⇒ BC)

Die Verbindung C, in der R21 die Bedeutung eines Wittigsalzes hat und eventuell vorhandene zusätzliche Carbonylgruppen geschützt sind, wird durch eine geeignete Base wie z. B. n-Butyllithium, Lithiumdiisopropylamid, Kalium- tert.-butanolat, Natrium- oder Lithium-hexamethyldisilazid deprotoniert und mit einer Verbindung B, worin V die Bedeutung von Sauerstoff und W die Bedeutung zweier Alkoxygruppen OR19, einer C2-C10-Alkylen-α,ω- dioxygruppe, die geradkettig oder verzweigt sein kann oder H/OR18 hat, umsetzt.The compound C, in which R 21 has the meaning of a Wittigsalzes and any additional carbonyl groups that may be present are protected by a suitable base such as. B. n-butyllithium, lithium diisopropylamide, potassium tert-butoxide, sodium or lithium hexamethyldisilazide deprotonated and with a compound B, in which V is oxygen and W is two alkoxy groups OR 19 , one C 2 -C 10 - Alkylene-α, ω-dioxy group, which can be straight-chain or branched or has H / OR 18 , is implemented.

Teilfragmente der allgemeinen Formel ABC (AB + C)
Partial fragments of the general formula ABC (AB + C)

worin R1a', R1b', R2a', R2b', R3a, R4, R5, R6, R7, R8, R13, R14, E, U und Z die bereits genannten Bedeutungen haben und PG14 ein Wasserstoffatom oder eine Schutzgruppe PG darstellt, werden aus den zuvor beschriebenen Fragmenten AB und C nach dem in Schema 4 und Schema 5 gezeigten Verfahren erhalten. wherein R 1a ' , R 1b' , R 2a ' , R 2b' , R 3a , R 4 , R 5 , R 6 , R 7 , R 8 , R 13 , R 14 , E, U and Z have the meanings already mentioned and PG 14 represents a hydrogen atom or a protective group PG, are obtained from the fragments AB and C described above by the process shown in Scheme 4 and Scheme 5.

Schema 4 Scheme 4

Schritt ac (AB + C ⇒ ABC)Step ac (AB + C ⇒ ABC)

Die Verbindung C, in der R21 die Bedeutung eines Wittigsalzes hat und eventuell vorhandene zusätzliche Carbonylgruppen geschützt sind, wird durch eine geeignete Base wie z. B. n-Butyllithium, Lithiumdiisopropylamid, Kalium- tert.-butanolat, Natrium- oder Lithium-hexamethyldisilazid deprotoniert und mit einer Verbindung AB, worin V die Bedeutung eines Sauerstoffatomes hat, umgesetzt.The compound C, in which R 21 has the meaning of a Wittigsalzes and any additional carbonyl groups that may be present are protected by a suitable base such as. B. n-butyllithium, lithium diisopropylamide, potassium tert-butoxide, sodium or lithium hexamethyldisilazide deprotonated and reacted with a compound AB, in which V has the meaning of an oxygen atom.

Schema 5 Scheme 5

Schritt ad (A+BC ⇒ ABC)Step ad (A + BC ⇒ ABC)

Die Verbindung BC, worin W die Bedeutung eines Sauerstoffatomes hat und eventuell vorhandene zusätzliche Carbonylgruppen geschützt sind, wird mit dem Enolat einer Carbonylverbindung der allgemeinen Formel A alkyliert. Das Enolat wird durch Einwirkung starker Basen wie z. B. Lithiumdiisopropylamid, Lithiumhexamethyldisilazan bei niedrigen Temperaturen hergestellt. The compound BC, in which W has the meaning of an oxygen atom and any additional carbonyl groups that may be present are protected with the Alkylated enolate of a carbonyl compound of the general formula A. The enolate is by the action of strong bases such. B. lithium diisopropylamide, Lithium hexamethyldisilazane produced at low temperatures.  

Schritt ae (ABC ⇒ I)Step ae (ABC ⇒ I)

Die Verbindungen ABC, in denen R13 eine Carbonsäure CO2H und PG12 ein Wasserstoffatom darstellt, setzt man nach den, dem Fachmann bekannten Methoden für die Bildung großer Macrolide zu Verbindungen der Formel I, in denen Y die Bedeutung eines Sauerstoffatomes besitzt, um. Bevorzugt wird die in "Reagents for Organic Synthesis, Vol. 16, p 353" beschriebene Methode unter Verwendung von 2,4,6-Trichlorbenzoesäurechlorid und geeigneten Basen wie z. B. Triethylamin, 4-Dimethylaminopyridin, Natriumhydrid.The compounds ABC, in which R 13 is a carboxylic acid CO 2 H and PG 12 is a hydrogen atom, are converted according to the methods known to the person skilled in the art for the formation of large macrolides to give compounds of the formula I in which Y has the meaning of an oxygen atom . The method described in "Reagents for Organic Synthesis, Vol. 16, p 353" is preferred using 2,4,6-trichlorobenzoic acid chloride and suitable bases such as, for. B. triethylamine, 4-dimethylaminopyridine, sodium hydride.

Schritt af (ABC ⇒ I)Step af (ABC ⇒ I)

Die Verbindungen ABC, in denen R13 eine Gruppe CH2OH und PG12 ein Wasserstoffatom darstellt, lassen sich vorzugsweise unter Verwendung von Triphenylphosphin und Azodiestern wie beispielsweise Azodicarbonsäurediethylester zu Verbindungen der Formel I, in denen Y die Bedeutung zweier Wasserstoffatome hat, umsetzen.The compounds ABC, in which R 13 represents a group CH 2 OH and PG 12 represents a hydrogen atom, can preferably be converted to compounds of the formula I, in which Y has the meaning of two hydrogen atoms, using triphenylphosphine and azodiesters such as, for example, diethyl azodicarboxylate.

Die Verbindungen ABC, in denen R13 eine Gruppe CH2-Hal oder CH2OSO2Alkyl oder CH2OSO2Aryl oder CH2OSO2Aralkyl und PG12 ein Wasserstoffatom darstellt, fassen sich nach Deprotonierung mit geeigneten Basen wie beispielsweise Natriumhydrid, n-Buthyllithium, 4- Dimethylaminopyridin, Hünig-Base, Alkylihexamethyldisilazanen zu Verbindungen der Formel I, in denen Y die Bedeutung zweier Wasserstoffatome hat, zyklisieren.The compounds ABC, in which R 13 represents a group CH 2 -Hal or CH 2 OSO 2 alkyl or CH 2 OSO 2 aryl or CH 2 OSO 2 aralkyl and PG 12 represents a hydrogen atom, can be deprotonated with suitable bases such as sodium hydride, Cyclize n-butyllithium, 4-dimethylaminopyridine, Hünig base, alkylihexamethyldisilazanes to give compounds of the formula I in which Y has the meaning of two hydrogen atoms.

Die flexible Funktionalisierung der beschriebenen Bausteine A, B und C gewährleistet auch eine von dem oben beschriebenen Verfahren abweichende Verknüpfungsreihenfolge, die zu den Bausteinen ABC führt. Diese Verfahren sind in der folgenden Tabelle zusammengestellt:
The flexible functionalization of the described modules A, B and C also ensures a linking sequence which deviates from the method described above and which leads to the modules ABC. These procedures are summarized in the following table:

Nach diesen Verfahren lassen sich die Bausteine A, B und C, wie in Schema 6 angegeben, verknüpfen:Using these methods, building blocks A, B and C can be created as in Scheme 6 specified, link:

Schema 6 Scheme 6

Freie Hydroxylgruppen in I, A, B, C, AB, BC, ABC können durch Veretherung oder Veresterung, freie Carbonylgruppen durch Ketalisierung, Enoletherbildung oder Reduktion weiter funktionell abgewandelt sein.Free hydroxyl groups in I, A, B, C, AB, BC, ABC can be etherified or esterification, free carbonyl groups by ketalization, enol ether formation or reduction can be further functionally modified.

Die Erfindung betrifft alle Stereoisomeren dieser Verbindungen und auch deren Gemische.The invention relates to all stereoisomers of these compounds and also theirs Mixtures.

Die Erfindung betrifft weiterhin alle Prodrugformulierungen dieser Verbindungen, d. h. alle Verbindungen, die in vivo eine bioaktive Wirkstoffkomponente der allgemeinen Formel I freisetzen. The invention further relates to all prodrug formulations of these compounds, d. H. all compounds that are a bioactive component of the active ingredient in vivo release general formula I.  

Biologische Wirkungen und Anwendungsbereiche der neuen DerivateBiological effects and areas of application of the new derivatives

Die neuen Verbindungen der Formel I sind wertvolle Pharmaka. Sie interagieren mit Tubulin, indem sie gebildete Mikrotubuli stabilisieren und sind somit in der Lage, die Zellteilung phasenspezifisch zu beeinflussen. Dies betrifft vor allem schnell wachsende, neoplastische Zellen, deren Wachstum durch interzelluläre Regelmechnismen weitgehend unbeeinflußt ist. Wirkstoffe dieser Art sind prinzipiell geeigne 51117 00070 552 001000280000000200012000285915100600040 0002019954228 00004 50998t zur Behandlung maligner Tumoren. Als Anwendungsbereich seien beispielweise genannt die Therapie von Ovarial-, Magen-, Colon-, Adeno-, Brust-, Lungen-, Kopf- und Nacken-Karzinomen, dem malignen Melanom, der akuten lymphozytären und myelocytären Leukämie. Die erfindungsgemäßen Verbindungen eignen sich aufgrund ihrer Eigenschaften prinzipiell zur Anti- Angiogenese-Therapie sowie zur Behandlung chronischer entzündlicher Erkrankungen wie beispielsweise der Psoriasis, der multiplen Sklerose oder der Arthritis. Zur Vermeidung unkontrollierter Zellwucherungen an sowie der besseren Verträglichkeit von medizinischen Implantaten lassen sie sich prinzipiell in die hierfür verwendeten polymeren Materialien auf- bzw. einbringen. Die erfindungsgemäßen Verbindungen können alleine oder zur Erzielung additiver oder synergistischer Wirkungen in Kombination mit weiteren in der Tumortherapie anwendbaren Prinzipien und Substanzklassen verwendet werden.The new compounds of formula I are valuable pharmaceuticals. They interact with tubulin, by stabilizing microtubules formed and are thus in the Able to influence the cell division in a phase-specific manner. This affects above all fast growing, neoplastic cells whose growth is due to intercellular Control mechanisms are largely unaffected. Active substances of this type are principally suitable 51117 00070 552 001000280000000200012000285915100600040 0002019954228 00004 50998t for the treatment of malignant tumors. As a scope the therapy of ovarian, stomach, colon, adeno, Breast, lung, head and neck carcinomas, the malignant melanoma, the acute lymphocytic and myelocytic leukemia. The invention Due to their properties, compounds are principally suitable for Angiogenesis therapy as well as for the treatment of chronic inflammatory Diseases such as psoriasis, multiple sclerosis or Arthritis. To avoid uncontrolled cell growth on and the They can be better tolerated by medical implants in principle apply or incorporate into the polymeric materials used for this. The compounds according to the invention can be used alone or to achieve them additive or synergistic effects in combination with other in the Principles and classes of substances used in tumor therapy become.

Als Beispiele seien genannt die Kombination mit
Examples include the combination with

  • - Platinkomplexen wie z. B. Cisplatin, Carboplatin,- Platinum complexes such as B. cisplatin, carboplatin,
  • - interkalierenden Substanzen z. B. aus der Klasse der Anthracycline wie z. B. Doxorubicin oder aus der Klasse der Antrapyrazole wie z. B. CI-941,- Intercalating substances e.g. B. from the class of anthracyclines such. B. Doxorubicin or from the class of antrapyrazoles such. B. CI-941,
  • - mit Tubulin interagierenden Substanzen z. B. aus der Klasse der Vinka- Alkaloide wie z. B. Vineristin, Vinbfastin oder aus der Klasse der Taxane wie z. B. Taxol, Taxotere oder aus der Klasse der Makrolide wie z. B. Rhizoxin oder andere Verbindungen wie z. B. Colchicin, Combretastatin A-4, Discodermolid und seine Analoga,- substances interacting with tubulin z. B. from the class of Vinka- Alkaloids such as B. Vinerist, Vinbfastin or from the class of taxanes such as e.g. B. Taxol, Taxotere or from the class of macrolides such. B. Rhizoxin or other connections such. B. colchicine, combretastatin A-4, Discodermolide and its analogues,
  • - DNA Topoisomeraseinhibitoren wie z. B. Camptothecin, Etoposid, Topotecan, Teniposid,- DNA topoisomerase inhibitors such as B. camptothecin, etoposide, topotecan, Teniposide,
  • - Folat- oder Pyrimidin-Antimetaboliten wie z. B. Lometrexol, Gemcitubin, - Folate or pyrimidine antimetabolites such as B. lometrexol, gemcitubin,  
  • - DNA alkylierenden Verbindungen wie z. B. Adozelesin, Dystamycin A,- DNA alkylating compounds such. B. adozelesin, dystamycin A,
  • - Inhibitoren von Wachstumsfaktoren (z. B. von PDGF, EGF, TGFb, EGF) wie z. B. Somatostatin, Suramin, Bombesin-Antagonisten,- Inhibitors of growth factors (e.g. PDGF, EGF, TGFb, EGF) such as e.g. B. somatostatin, suramin, bombesin antagonists,
  • - Inhibitoren der Protein Tyrosin Kinase oder der Protein Kinasen A oder C wie z. B. Erbstatin, Genistein, Staurosporin, Ilmofosin, 8-CI-cAMP,- Inhibitors of protein tyrosine kinase or protein kinases A or C as e.g. B. Erbstatin, Genistein, Staurosporin, Ilmofosin, 8-CI-cAMP,
  • - Antihormonen aus der Klasse der Antigestagene wie z. B. Mifepriston, Onapriston oder aus der Klasse der Antiöstrogene wie z. B. Tamoxifen oder aus der Klasse der Antiandrogene wie z. B. Cyproteronacetat,- Anti-hormones from the class of anti-gestagens such. B. mifepristone, Onapriston or from the class of anti-estrogens such. B. Tamoxifen or from the class of antiandrogens such as B. cyproterone acetate,
  • - Metastasen inhibierenden Verbindungen z. B. aus der Klasse der Eicosanoide wie z. B. PGI2, PGE1, 6-Oxo-PGE1 sowie deren stabiler Derivate (z. B. Iloprost, Cicaprost, Misoprostol).- Metastasis inhibiting compounds z. B. from the class of eicosanoids such. B. PGI 2 , PGE 1 , 6-oxo-PGE 1 and their stable derivatives (e.g. Iloprost, Cicaprost, Misoprostol).
  • - Inhibitoren onkogener RAS-Proteine, welche die mitotische Signaltransduktion beeinflussen wie beispielsweise Inhibitoren der Farnesyl- Protein-Transferase,- Inhibitors of oncogenic RAS proteins, which mitotic Signal transduction affect such as inhibitors of farnesyl Protein transferase,
  • - natürlichen oder künstlich erzeugten Antikörpern, die gegen Faktoren bzw. deren Rezeptoren, die das Tumorwachstum fördern, gerichtet sind wie beispielsweise der erbB2-Antikörper.- natural or artificially produced antibodies that are against factors or whose receptors that promote tumor growth are directed like for example the erbB2 antibody.

Die Erfindung betrifft auch Arzneimittel auf Basis der pharmazeutisch verträglichen, d. h. in den verwendeten Dosen nicht toxischen Verbindungen der allgemeinen Formel I, gegebenenfalls zusammen mit den üblichen Hilfs- und Trägerstoffen.The invention also relates to pharmaceuticals based on the pharmaceutical tolerable, d. H. in the used doses of non-toxic compounds general formula I, optionally together with the usual auxiliaries and Carriers.

Die erfindungsgemäßen Verbindungen können nach an sich bekannten Methoden der Galenik zu pharmazeutischen Präparaten für die enterale, percutane, parenterale oder lokale Applikation verarbeitet werden. Sie können in Form von Tabletten, Dragees, Gelkapseln, Granulaten, Suppositorien, Implantaten, injizierbaren sterilen wäßrigen oder öligen Lösungen, Suspensionen oder Emulsionen, Salben, Cremes und Gelen verabreicht werden.The compounds of the invention can be prepared according to known methods Methods of galenics for pharmaceutical preparations for enteral, percutaneous, parenteral or local application can be processed. You can in Form of tablets, coated tablets, gel capsules, granules, suppositories, Implants, injectable sterile aqueous or oily solutions, Suspensions or emulsions, ointments, creams and gels administered become.

Der oder die Wirkstoffe können dabei mit den in der Galenik üblichen Hilfsstoffen wie z. B. Gummiarabikum, Talk, Stärke, Mannit, Methylcellulose, Laktose, Tensiden wie Tweens oder Myrj, Magnesiumstearat, wäßrigen oder nicht wäßrigen Trägern, Paraffinderivaten, Netz-, Dispergier-, Emulgier-, Konservierungsmitteln und Aromastoffen zur Geschmackskorrektur (z. B. etherischen Ölen) gemischt werden.The active ingredient (s) can be used with the galenics Excipients such as B. gum arabic, talc, starch, mannitol, methyl cellulose, Lactose, surfactants such as tweens or myrj, magnesium stearate, aqueous or  non-aqueous carriers, paraffin derivatives, wetting, dispersing, emulsifying, Preservatives and flavorings for flavor correction (e.g. essential oils) are mixed.

Die Erfindung betrifft somit auch pharmazeutische Zusammensetzungen, die als Wirkstoff zumindest eine erfindungsgemäße Verbindung enthalten. Eine Dosiseinheit enthält etwa 0,1-100 mg Wirkstoff(e). Die Dosierung der erfindungsgemäßen Verbindungen liegt beim Menschen bei etwa 0,1-1000 mg pro Tag.The invention thus also relates to pharmaceutical compositions which as Contain active ingredient at least one compound of the invention. A Dose unit contains about 0.1-100 mg of active ingredient (s). The dosage of the Compounds according to the invention are about 0.1-1000 mg in humans per day.

Die nachfolgenden Beispiele dienen der näheren Erläuterung der Erfindung, ohne sie darauf einschränken zu wollen: The following examples serve to explain the invention in more detail, without wanting to limit it:  

Beispiel 1example 1 (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion(4S, 7R, 8S, 9S, 13Z, 16S (E)) - 4,8-Dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) - 1-oxa-5,5,9,13-tetramethyl-7- (but-3-in-1-yl) cyclohexadec-13-en-2,6-dione

Herstellung von (4S(4R,5S,6S,10E/Z,13S,14E))-4-(13-Hydroxy-5-(tetrahydro- 2H-pyran-2-yloxy)-2,6,10,14-tetramethyl-3-oxo-15-(2-pyridyl)-4-(but-3-in-1-yl)- undec-6-in-2-yl)-2,2-dimethyl-[1,3]dioxan.Preparation of (4S (4R, 5S, 6S, 10E / Z, 13S, 14E)) - 4- (13-hydroxy-5- (tetrahydro- 2H-pyran-2-yloxy) -2,6,10,14-tetramethyl-3-oxo-15- (2-pyridyl) -4- (but-3-in-1-yl) - undec-6-in-2-yl) -2,2-dimethyl- [1,3] dioxane.

Variante I Variant I Beispiel 1aExample 1a (3RS,4S)-4-(2-Methyl-3-hydroxy-8-(trimethylsily)-oct-7-in-2-yl)-2,2-dimethyl- [1,3]dioxan(3RS, 4S) -4- (2-methyl-3-hydroxy-8- (trimethylsily) oct-7-in-2-yl) -2,2-dimethyl- [1,3] dioxane

Die Lösung von 6,33 g (34 mmol) (4S)-4-(2-Methyl-1-oxoprop-2-yl)-2,2- dimethyl-[1,3]dioxan, das man in Analogie zu den in DE 197 51 200.3 beschriebenen Verfahren hergestellt hat, in 10 ml wasserfreiem Tetrahydrofuran versetzt man portionsweise unter einer Atmosphäre aus trockenem Argon mit der Lösung von insgesamt 50 mmol 5-Trimethylsilyl-pent-4-in-1-yl- magnesiumbromid in Tetrahydrofuran, läßt auf 60°C erwärmen und rührt 1,5 Stunden. Man gießt auf Wasser und extrahiert mehrfach mit Ethylacetat. Die vereinigten organischen Extrakte wäscht man mit Wasser und gesättigter Natriumchloridlösung und trocknet über Natriumsulfat. Den nach Filtration und Lösungsmittelabzug erhaltenen Rückstand reinigt man durch Chromatographie an feinem Kieselgel mit einem Gradientensystem aus n-Hexan und Ethylacetat. Isoliert werden 6,22 g (19 mmol, 56%) der chromatographisch trennbaren 3R- und 3S-Epimeren der Titelverbindung sowie 1,35 g (4S)-4-(2-Methyl-1-hydroxy- prop-2-yl)-2,2-dimethyl-[1,3]dioxan jeweils als farbloses Öl.
1H-NMR (CDCl3): δ = 0,14 (9H), 0,73+0,88 (3H), 0,91 (3H), 1,28-1,93 (12H), 2,21-2,33 (2H), 3,40-3,72 (2H), 3,80-4,03 (3H) ppm.The solution of 6.33 g (34 mmol) of (4S) -4- (2-methyl-1-oxoprop-2-yl) -2,2-dimethyl- [1,3] dioxane, which is obtained in analogy to the process described in DE 197 51 200.3, 10 ml of anhydrous tetrahydrofuran are added in portions under a dry argon atmosphere with a solution of a total of 50 mmol of 5-trimethylsilyl-pent-4-yn-1-yl-magnesium bromide in tetrahydrofuran Warm to 60 ° C and stir for 1.5 hours. It is poured onto water and extracted several times with ethyl acetate. The combined organic extracts are washed with water and saturated sodium chloride solution and dried over sodium sulfate. The residue obtained after filtration and removal of solvent is purified by chromatography on fine silica gel using a gradient system composed of n-hexane and ethyl acetate. 6.22 g (19 mmol, 56%) of the chromatographically separable 3R and 3S epimers of the title compound and 1.35 g (4S) -4- (2-methyl-1-hydroxy-prop-2-yl) are isolated -2,2-dimethyl- [1,3] dioxane each as a colorless oil.
1 H NMR (CDCl 3 ): δ = 0.14 (9H), 0.73 + 0.88 (3H), 0.91 (3H), 1.28-1.93 (12H), 2.21 -2.33 (2H), 3.40-3.72 (2H), 3.80-4.03 (3H) ppm.

Beispiel 1bExample 1b (4S)-4-(2-Methyl-3-oxo-8-(trimethylsily)-oct-7-in-2-yl)-2,2-dimethyl-[1,3]dioxan(4S) -4- (2-Methyl-3-oxo-8- (trimethylsily) oct-7-in-2-yl) -2,2-dimethyl- [1,3] dioxane

Die Lösung von 6,22 g (19 mmol) eines Gemisches der nach Beispiel 1a dargestellten Verbindungen in 200 ml wasserfreiem Dichlormethan versetzt man mit Molekularsieb (4A, ca. 20 Kugeln), 4,01 g N-Methylmorpholino-N-oxid, 335 mg Tetrapropylammoniumperruthenat und rührt 16 Stunden bei 23°C unter einer Atmosphäre aus trockenem Argon. Man engt ein und reinigt das erhaltene Rohprodukt durch Chromatographie an feinem Kieselgel mit einem Gradientensystem aus n-Hexan und Ethylacetat. Isoliert werden 5,17 g (15,9 mmol, 84%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = 0,15 (9H), 1,07 (3H), 1,13 (3H), 1,28-1,36 (1H), 1,33 (3H), 1,41 (3H), 1,53-1,81 (3H), 2,22 (2H), 2,62 (2H), 3,85 (1H), 3,97 (1H), 4,06 (1H) ppm.The solution of 6.22 g (19 mmol) of a mixture of the compounds shown in Example 1a in 200 ml of anhydrous dichloromethane is mixed with molecular sieve (4A, approx. 20 spheres), 4.01 g of N-methylmorpholino-N-oxide, 335 mg of tetrapropylammonium perruthenate and stirred for 16 hours at 23 ° C under an atmosphere of dry argon. The mixture is concentrated and the crude product obtained is purified by chromatography on fine silica gel using a gradient system composed of n-hexane and ethyl acetate. 5.17 g (15.9 mmol, 84%) of the title compound are isolated as a colorless oil.
1 H-NMR (CDCl 3 ): δ = 0.15 (9H), 1.07 (3H), 1.13 (3H), 1.28-1.36 (1H), 1.33 (3H), 1.41 (3H), 1.53-1.81 (3H), 2.22 (2H), 2.62 (2H), 3.85 (1H), 3.97 (1H), 4.06 ( 1H) ppm.

Beispiel 1cExample 1c (4S(4R,5S,6S,10RS))-4-(5-Hydroxy-2,6-dimethyl-3-oxo-4-(4-(trimethylsily)-but-3- in-1-yl)-10-[[diphenyl(1,1-dimethylethyl)silyl]oxy]-undec-2-yl)-2,2-dimethyl- [1,3]dioxan (A) und (4S(4S,5R,6S,10RS))-4-(5-Hydroxy-2,6-dimethyl-3-oxo-4-(4- (trimethylsily)-but-3-in-1-yl)-10-[[diphenyl(1,1-dimethylethyl)silyl]oxy]-undec-2-yl)- 2,2-dimethyl-[1,3]dioxan (B)(4S (4R, 5S, 6S, 10RS)) - 4- (5-Hydroxy-2,6-dimethyl-3-oxo-4- (4- (trimethylsily) but-3- in-1-yl) -10 - [[diphenyl (1,1-dimethylethyl) silyl] oxy] -undec-2-yl) -2,2-dimethyl- [1,3] dioxane (A) and (4S (4S, 5R, 6S, 10RS)) - 4- (5-hydroxy-2,6-dimethyl-3-oxo-4- (4- (trimethylsily) but-3-in-1-yl) -10 - [[diphenyl (1,1-dimethylethyl) silyl] oxy] -undec-2-yl) - 2,2-dimethyl- [1,3] dioxane (B)

Die Lösung von 1,33 ml Diisopropylamin in 35 ml wasserfreiem Tetrahydrofuran kühlt man unter einer Atmosphäre aus trockenem Argon auf -30°C, versetzt mit 4,28 ml einer 2,4 molaren Lösung von n-Butyllithium in n-Hexan und rührt noch 15 Minuten. Bei -78°C tropft man die Lösung von 2,87 g (8,84 mmol) der nach Beispiel 1c dargestellten Verbindung in 35 ml Tetrahydrofuran zu und läßt 1 Stunde reagieren. Anschließend versetzt man langsam mit der Lösung von 3,93 g (10,3 mmol) (2S,6RS)-2-Methyl-6-(tert.-butyl-diphenylsilyloxy)-heptanal, das man in Analogie zu den in DE 197 51 200.3 beschriebenen Verfahren hergestellt hat, in 35 ml Tetrahydrofuran und gießt nach 1 Stunde in gesättigte Ammoniumchloridlösung. Man verdünnt mit Wasser, extrahiert mehrfach mit Ethylacetat, wäscht die vereinigten organischen Extrakte mit gesättigter Natriumchloridlösung, trocknet über Natriumsulfat und engt im Vakuum ein. Nach Säulenchromatographie an Kieselgel mit einem Gradientensystem aus n- Hexan und Ethylacetat werden neben Ausgangsmaterial 2,40 g (3,39 mmol, 38%) der Titelverbindung A sowie 1,52 g (2,15 mmol, 24%) des Diastereomeren B erhalten.
1H-NMR (CDCl3) von A: δ = 0,16 (9H), 0,83 (3H), 1,00 (3H), 1,02 (3H), 1,04 (9H), 1,10-1,77 (10H), 1,28 (3H), 1,31 (3H), 1,37 (3H), 1,83-2,03 (2H), 2,19-2,38 (2H), 3,52 (1H), 3,62 (1H), 3,78-3,92 (2H), 3,98 (1H), 4,23 (1H), 7,30-7,46 (6H), 7,67 (4H) ppm.
1H-NMR (CDCl3) von B: δ = 0,13 (9H), 0,86+0,92 (3H), 0,95-1,77 (16H), 1,03 (9H), 1,21+1,25 (3H), 1,32 (3H), 1,40 (3H), 1,88-2,09 (2H), 2,26 (1H), 2,39 (1H), 3,29-3,54 (2H), 3,77-3,90 (2H), 3,96 (1H), 4,18 (1H), 7,31-7,46 (6H), 7,67 (4H) ppm.The solution of 1.33 ml of diisopropylamine in 35 ml of anhydrous tetrahydrofuran is cooled to -30 ° C. under an atmosphere of dry argon, mixed with 4.28 ml of a 2.4 molar solution of n-butyllithium in n-hexane and stirred 15 minutes. The solution of 2.87 g (8.84 mmol) of the compound shown in Example 1c in 35 ml of tetrahydrofuran is added dropwise at -78 ° C. and the mixture is left to react for 1 hour. The solution of 3.93 g (10.3 mmol) of (2S, 6RS) -2-methyl-6- (tert-butyl-diphenylsilyloxy) -heptanal, which is prepared analogously to that in DE 197 Has prepared the process described 200.3, in 35 ml of tetrahydrofuran and after 1 hour poured into saturated ammonium chloride solution. It is diluted with water, extracted several times with ethyl acetate, the combined organic extracts are washed with saturated sodium chloride solution, dried over sodium sulfate and concentrated in vacuo. After column chromatography on silica gel with a gradient system of n-hexane and ethyl acetate, in addition to the starting material, 2.40 g (3.39 mmol, 38%) of the title compound A and 1.52 g (2.15 mmol, 24%) of the diastereomer B are obtained .
1 H-NMR (CDCl 3 ) of A: δ = 0.16 (9H), 0.83 (3H), 1.00 (3H), 1.02 (3H), 1.04 (9H), 1, 10-1.77 (10H), 1.28 (3H), 1.31 (3H), 1.37 (3H), 1.83-2.03 (2H), 2.19-2.38 (2H ), 3.52 (1H), 3.62 (1H), 3.78-3.92 (2H), 3.98 (1H), 4.23 (1H), 7.30-7.46 (6H ), 7.67 (4H) ppm.
1 H NMR (CDCl 3 ) of B: δ = 0.13 (9H), 0.86 + 0.92 (3H), 0.95-1.77 (16H), 1.03 (9H), 1 , 21 + 1.25 (3H), 1.32 (3H), 1.40 (3H), 1.88-2.09 (2H), 2.26 (1H), 2.39 (1H), 3 , 29-3.54 (2H), 3.77-3.90 (2H), 3.96 (1H), 4.18 (1H), 7.31-7.46 (6H), 7.67 ( 4H) ppm.

Beispiel 1dExample 1d (4S(4R,5S,6S,10RS))-4-(2,6-Dimethyl-3-oxo-4-(4-trimethylsily-but-3-in-1-yl)-5- (tetrahydro-2H-pyran-2-yloxy)-10-[[diphenyl(1,1-dimethylethyl)silyl]oxy]-undec-2- yl)-2,2-dimethyl-[1,3]dioxan(4S (4R, 5S, 6S, 10RS)) - 4- (2,6-dimethyl-3-oxo-4- (4-trimethylsilybut-3-in-1-yl) -5- (tetrahydro-2H-pyran-2-yloxy) -10 - [[diphenyl (1,1-dimethylethyl) silyl] oxy] -undec-2- yl) -2,2-dimethyl- [1,3] dioxane

Die Lösung von 2,35 g (3,32 mmol) der nach Beispiel 1c dargestellten Verbindung A in 55 ml wasserfreiem Dichlormethan versetzt man unter einer Atmosphäre aus trockenem Argon mit 3,04 ml 3,4-Dihydro-2H-pyran, 0,67 g p- Toluolsulfonsäure und rührt 48 Stunden bei 23°C. Man gießt in eine gesättigte Natriumhydrogencarbonatlösung, trennt die organische Phase ab und trocknet über Natriumsulfat. Nach Filtration und Lösungsmittelabzug chromatographiert man den Rückstand an feinem Kieselgel mit einem Gemisch aus n-Hexan und Ethylacetat. Isoliert werden 2,29 g (2,89 mmol, 87%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = 0,05 (9H), 0,88-2,15 (28H), 1,03 (9H), 1,41 (3H), 1,59 (3H), 2,21-2,48 (1H), 3,31-4,53 (9H), 7,30-7,45 (6H), 7,69 (4H) ppm.The solution of 2.35 g (3.32 mmol) of the compound A prepared according to Example 1c in 55 ml of anhydrous dichloromethane is mixed with 3.04 ml of 3,4-dihydro-2H-pyran, 0.02 in an atmosphere of dry argon. 67 g of p-toluenesulfonic acid and stirred at 23 ° C. for 48 hours. It is poured into a saturated sodium bicarbonate solution, the organic phase is separated off and dried over sodium sulfate. After filtration and removal of solvent, the residue is chromatographed on fine silica gel with a mixture of n-hexane and ethyl acetate. 2.29 g (2.89 mmol, 87%) of the title compound are isolated as a colorless oil.
1 H-NMR (CDCl 3 ): δ = 0.05 (9H), 0.88-2.15 (28H), 1.03 (9H), 1.41 (3H), 1.59 (3H), 2.21-2.48 (1H), 3.31-4.53 (9H), 7.30-7.45 (6H), 7.69 (4H) ppm.

Beispiel 1eExample 1e (4S(4R,5S,6S,10RS))-4-(2,6-Dimethyl-10-hydroxy-3-oxo-5-(tetrahydro-2H- pyran-2-yloxy)-4-(but-3-in-1-yl)-undec-2-yl)-2,2-dimethyl-[1,3]dioxan(4S (4R, 5S, 6S, 10RS)) - 4- (2,6-dimethyl-10-hydroxy-3-oxo-5- (tetrahydro-2H- pyran-2-yloxy) -4- (but-3-yn-1-yl) -undec-2-yl) -2,2-dimethyl- [1,3] dioxane

Die Lösung von 2,48 g (3,13 mmol) der nach Beispiel 1d dargestellten Verbindung in 25 ml wasserfreiem Tetrahydrofuran versetzt man unter einer Atmosphäre aus trockenem Argon mit 12,5 ml einer 1 molaren Lösung von Tetrabutylammoniumfluorid in Tetrahydrofuran und rührt 4 Stunden bei 23°C. Man versetzt mit gesättigter Natriumhydrogencarbonatlösung, extrahiert mehrfach mit Ethylacetat, wäscht mit gesättigter Natriumchloridlösung und trocknet über Natriumsulfat. Den nach Filtration und Lösungsmittelabzug erhaltenen Rückstand reinigt man durch Chromatographie an feinem Kieselgel mit einem Gradientensystem aus n-Hexan und Ethylacetat. Isoliert werden 1,41 g (2,93 mmol, 94%) der Titelverbindung als farbloses Öl.The solution of 2.48 g (3.13 mmol) of that shown in Example 1d Compound in 25 ml of anhydrous tetrahydrofuran is added under a Atmosphere of dry argon with 12.5 ml of a 1 molar solution of Tetrabutylammonium fluoride in tetrahydrofuran and stirred for 4 hours at 23 ° C. Saturated sodium hydrogen carbonate solution is added and the mixture is extracted  several times with ethyl acetate, washed with saturated sodium chloride solution and dries over sodium sulfate. The one after filtration and removal of solvent the residue obtained is purified by chromatography on fine silica gel with a gradient system of n-hexane and ethyl acetate. 1.41 g are isolated (2.93 mmol, 94%) of the title compound as a colorless oil.

Beispiel 1fExample 1f (4S(4R,5S,6S,10RS))-4-(2,6-Dimethyl-3,10-dioxo-5-(tetrahydro-2H-pyran-2- yloxy)-4-(but-3-in-1-yl)-undec-2-yl)-2,2-dimethyl-[1,3]dioxan(4S (4R, 5S, 6S, 10RS)) - 4- (2,6-dimethyl-3,10-dioxo-5- (tetrahydro-2H-pyran-2- yloxy) -4- (but-3-yn-1-yl) -undec-2-yl) -2,2-dimethyl- [1,3] dioxane

In Analogie zu Beispiel 1b setzt man 1,27 g (2,63 mmol) der nach Beispiel 1e dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 1,14 g (2,38 mmol, 91%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = 0,95-2,48 (29H), 0,98+1,01 (3H), 1,42 (3H), 2,13 (3H), 3,29-3,47 (2H), 3,64-4,04 (4H), 4,20+4,32 (1H), 4,39+4,50 (1H) ppm.Analogously to Example 1b, 1.27 g (2.63 mmol) of the compound shown in Example 1e is reacted and, after workup and purification, 1.14 g (2.38 mmol, 91%) of the title compound is isolated as a colorless oil.
1 H NMR (CDCl 3 ): δ = 0.95-2.48 (29H), 0.98 + 1.01 (3H), 1.42 (3H), 2.13 (3H), 3.29 -3.47 (2H), 3.64-4.04 (4H), 4.20 + 4.32 (1H), 4.39 + 4.50 (1H) ppm.

Beispiel 1gExample 1g (4S(4R,5S,6S,10E/Z,13S,14E))-4-(13-[[Diphenyl(1,1-dimethylethyl)silyl]oxy]-5- (tetrahydro-2H-pyran-2-yloxy)-2,6,10,14-tetramethyl-3-oxo-15-(2-pyridyl)-4-(but- 3-in-1-yl)-pentadec-2-yl)-2,2-dimethyl-[1,3]dioxan(4S (4R, 5S, 6S, 10E / Z, 13S, 14E)) - 4- (13 - [[Diphenyl (1,1-dimethylethyl) silyl] oxy] -5- (tetrahydro-2H-pyran-2-yloxy) -2,6,10,14-tetramethyl-3-oxo-15- (2-pyridyl) -4- (but- 3-in-1-yl) pentadec-2-yl) -2,2-dimethyl- [1,3] dioxane

Die Suspension von 2,87 g (3,57 mmol) (5E,3S)-[3-[[(1,1- Dimethylethyl)diphenylsilyl]oxy]-4-methyl-5-(2-pyridyl)-pent-4-en-1-yl]-triphenyl- phosphoniumiodid, das man in Analogie zu den in DE 197 51 200.3 beschriebenen Verfahren hergestellt hat, in 11 ml wasserfreiem Tetrahydrofuran versetzt man bei 0°C unter einer Atmosphäre aus trockenem Argon mit 2,72 ml einer 1,6 M Lösung von n-Butyllithium in n-Hexan und läßt auf 23°C erwärmen. Zu der roten Lösung tropft man langsam die Lösung von 1,14 g (2,38 mmol) der nach Beispiel 1f dargestellten Verbindung in 11 ml Tetrahydrofuran, läßt 2 Stunden rühren, gießt auf gesättigte Ammmoniumchloridlösung und extrahiert mehrfach mit Ethylacetat. Die vereinigten organischen Extrakte trocknet man über Natriumsulfat und engt im Vakuum ein. Nach Säulenchromatographie an Kieselgel mit einem Gradientensystem aus n-Hexan und Ethylacetat werden neben 20% Ausgangsmaterial 860 mg (0,98 mmol, 41%) der Titelverbindung erhalten.
1H-NMR (CDCl3): δ = 0,82-2,41 (41H), 1,05 (9H), 2,00 (3H), 3,23-3,45 (2H), 3,60-4,02 (3H), 4,08-4,51 (3H), 4,92-5,24 (1H), 6,16-6,76 (1H), 6,92-7,08 (2H), 7,21-7,43 (6H), 7,49-7,72 (5H), 8,55 (1H) ppm.The suspension of 2.87 g (3.57 mmol) (5E, 3S) - [3 - [[(1,1-dimethylethyl) diphenylsilyl] oxy] -4-methyl-5- (2-pyridyl) -pent- 4-en-1-yl] -triphenyl-phosphonium iodide, which has been prepared analogously to the processes described in DE 197 51 200.3, in 2. 1 ml of anhydrous tetrahydrofuran is mixed with 2.72 at 0 ° C. under an atmosphere of dry argon ml of a 1.6 M solution of n-butyllithium in n-hexane and allowed to warm to 23 ° C. The solution of 1.14 g (2.38 mmol) of the compound shown in Example 1f in 11 ml of tetrahydrofuran is slowly added dropwise to the red solution, the mixture is stirred for 2 hours, poured onto saturated ammonium chloride solution and extracted several times with ethyl acetate. The combined organic extracts are dried over sodium sulfate and concentrated in vacuo. After column chromatography on silica gel with a gradient system of n-hexane and ethyl acetate, 860 mg (0.98 mmol, 41%) of the title compound are obtained in addition to 20% of the starting material.
1 H NMR (CDCl 3 ): δ = 0.82-2.41 (41H), 1.05 (9H), 2.00 (3H), 3.23-3.45 (2H), 3.60 -4.02 (3H), 4.08-4.51 (3H), 4.92-5.24 (1H), 6.16-6.76 (1H), 6.92-7.08 (2H ), 7.21-7.43 (6H), 7.49-7.72 (5H), 8.55 (1H) ppm.

Beispiel 1hExample 1h Variante IVariant I (4S(4R,5S,6S,10E/Z,13S,14E))-4-(13-Hydroxy-5- (tetrahydro-2H-pyran-2-yloxy)-2,6,10,14-tetramethyl-3-oxo-15-(2-pyridyl)-4-(but- 3-in-1-yl)-pentadec-2-yl)-2,2-dimethyl-[1,3]dioxan(4S (4R, 5S, 6S, 10E / Z, 13S, 14E)) - 4- (13-hydroxy-5- (tetrahydro-2H-pyran-2-yloxy) -2,6,10,14-tetramethyl-3-oxo-15- (2-pyridyl) -4- (but- 3-in-1-yl) pentadec-2-yl) -2,2-dimethyl- [1,3] dioxane

In Analogie zu Beispiel 1b setzt man 482 mg (550 µmol) der nach Beispiel 1g dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 256 mg (401 µmol, 73%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = 0,88-2,48 (35H), 1,42 (3H), 1,64+1,72 (3H), 2,08 (3H), 3,29-3,47 (2H), 3,64-4,04 (4H), 4,12-4,35 (2H), 4,41+4,51 (1H), 5,20 (1H), 6,59 (1H), 7,09 (1H), 7,23 (1H), 7,63 (1H), 8,60 (1H) ppm.Analogously to Example 1b, 482 mg (550 μmol) of the compound shown in Example 1g is reacted and, after workup and purification, 256 mg (401 μmol, 73%) of the title compound is isolated as a colorless oil.
1 H NMR (CDCl 3 ): δ = 0.88-2.48 (35H), 1.42 (3H), 1.64 + 1.72 (3H), 2.08 (3H), 3.29 -3.47 (2H), 3.64-4.04 (4H), 4.12-4.35 (2H), 4.41 + 4.51 (1H), 5.20 (1H), 6, 59 (1H), 7.09 (1H), 7.23 (1H), 7.63 (1H), 8.60 (1H) ppm.

Herstellung von (4S(4R,5S,6S,10E/Z,13S,14E))-4-(13-Hydroxy-5-(tetrahydro- 2H-pyran-2-yloxy)-2,6,10,14-tetramethyl-3-oxo-15-(2-pyridyl)-4-(but-3-in-1-yl)- pentadec-2-yl)-2,2-dimethyl-[1,3]dioxan.Preparation of (4S (4R, 5S, 6S, 10E / Z, 13S, 14E)) - 4- (13-hydroxy-5- (tetrahydro- 2H-pyran-2-yloxy) -2,6,10,14-tetramethyl-3-oxo-15- (2-pyridyl) -4- (but-3-in-1-yl) - pentadec-2-yl) -2,2-dimethyl- [1,3] dioxane.

Variante IIVariant II Beispiel 1iExample 1i (4S(4R,5S,6S,10E/Z,13S,14E))-4-(13-([Diphenyl(1,1-dimethylethyl)silyl]oxy]-5- hydroxy-2,6,10,14-tetramethyl-3-oxo-15-(2-pyridyl)-4-(4-(trimethylsilyl)-but-3-in- 1-yl)-pentadec-2-yl)-2,2-dimethyl-[1,3]dioxan (A) und (4S(4S,5R,6S,10E/Z,13S,14E))-4-(13-[[Diphenyl(1,1-dimethylethyl)silyl]oxy]-5- hydroxy-2,6,10,14-tetramethyl-3-oxo-15-(2-pyridyl)-4-(4-(trimethylsilyl)-but-3-in- 1-yl)-pentadec-2-yl)-2,2-dimethyl-[1,3]dioxan (B)(4S (4R, 5S, 6S, 10E / Z, 13S, 14E)) - 4- (13 - ([Diphenyl (1,1-dimethylethyl) silyl] oxy] -5- hydroxy-2,6,10,14-tetramethyl-3-oxo-15- (2-pyridyl) -4- (4- (trimethylsilyl) but-3-in- 1-yl) -pentadec-2-yl) -2,2-dimethyl- [1,3] dioxane (A) and (4S (4S, 5R, 6S, 10E / Z, 13S, 14E)) - 4- (13 - [[Diphenyl (1,1-dimethylethyl) silyl] oxy] -5- hydroxy-2,6,10,14-tetramethyl-3-oxo-15- (2-pyridyl) -4- (4- (trimethylsilyl) but-3-in- 1-yl) -pentadec-2-yl) -2,2-dimethyl- [1,3] dioxane (B)

In Analogie zu Beispiel 1c setzt man 2,85 g (8,78 mmol) der nach Beispiel 1b dargestellten Verbindung mit 3,62 g (6,71 mmol) (2S,6E/Z,9S,10E)-2,6,10- Trimethyl-9-[[diphenyl(1,1-dimethylethyl)silyl]oxy]-1-oxo-11-(2-pyridyl)-undeca- 6,10-dien, das man in Analogie zu den in DE 197 51 200.3 beschriebenen Verfahren hergestellt hat, um und isoliert nach Aufarbeitung und Reinigung neben Ausgangsmaterial 1,28 g (1,48 mmol, 22%) der Titelverbindung A sowie 1,73 g (2,00 mmol, 30%) der Titelverbindung B jeweils als farbloses Öl.
1H-NMR (CDCl3) von A: δ = 0,13 (9H), 0,86-2,52 (36H), 1,08 (9H), 1,42+1,58 (3H), 2,01 (3H), 3,32-4,85 (9H), 5,00 (1H), 6,23 (1H), 6,97-7,09 (2H), 7,21-7,45 (6H), 7,57 (1H), 7,61-7,75 (4H), 8,56 (1H) ppm.
1H-NMR (CDCl3) von B: δ = 0,12 (9H), 0,77-2,53 (36H), 1,08 (9H), 1,38+1,62 (3H), 2,00 (3H), 3,23-4,86 (9H), 5,02 (1H), 6,23 (1H), 6,96-7,09 (2H), 7,19-7,47 (6H), 7,53-7,76 (5H), 8,57 (1H) ppm.In analogy to example 1c, 2.85 g (8.78 mmol) of the compound shown in example 1b is mixed with 3.62 g (6.71 mmol) (2S, 6E / Z, 9S, 10E) -2.6, 10- Trimethyl-9 - [[diphenyl (1,1-dimethylethyl) silyl] oxy] -1-oxo-11- (2-pyridyl) -undeca- 6,10-diene, which is analogous to that described in DE 197 51 200.3 has prepared the process to and isolated after workup and purification in addition to starting material 1.28 g (1.48 mmol, 22%) of the title compound A and 1.73 g (2.00 mmol, 30%) of the title compound B in each case as a colorless oil.
1 H NMR (CDCl 3 ) of A: δ = 0.13 (9H), 0.86-2.52 (36H), 1.08 (9H), 1.42 + 1.58 (3H), 2 , 01 (3H), 3.32-4.85 (9H), 5.00 (1H), 6.23 (1H), 6.97-7.09 (2H), 7.21-7.45 ( 6H), 7.57 (1H), 7.61-7.75 (4H), 8.56 (1H) ppm.
1 H NMR (CDCl 3 ) of B: δ = 0.12 (9H), 0.77-2.53 (36H), 1.08 (9H), 1.38 + 1.62 (3H), 2 , 00 (3H), 3.23-4.86 (9H), 5.02 (1H), 6.23 (1H), 6.96-7.09 (2H), 7.19-7.47 ( 6H), 7.53-7.76 (5H), 8.57 (1H) ppm.

Beispiel 1jExample 1j (4S(4R,5S,6S,10E/Z,13S,14E))-4-(13-[[Diphenyl(1,1-dimethylethyl)silyl]oxy]-5- (tetrahydro-2H-pyran-2-yloxy)-2,6,10,14-tetramethyl-3-oxo-15-(2-pyridyl)-4-(4- (trimethylsilyl)-but-3-in-1-yl)-undec-6-in-2-yl)-2,2-dimethyl-[1,3]dioxan(4S (4R, 5S, 6S, 10E / Z, 13S, 14E)) - 4- (13 - [[Diphenyl (1,1-dimethylethyl) silyl] oxy] -5- (tetrahydro-2H-pyran-2-yloxy) -2,6,10,14-tetramethyl-3-oxo-15- (2-pyridyl) -4- (4- (trimethylsilyl) but-3-in-1-yl) -undec-6-in-2-yl) -2,2-dimethyl- [1,3] dioxane

In Analogie zu Beispiel 1d setzt man 1,16 g (1,34 mmol) der nach Beispiel 1i dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 1,12 g (1,18 mmol, 88%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = 0,13 (9H), 0,86-2,52 (39H), 1,08 (9H), 2,01 (3H), 3,32-4,85 (9H), 5,00 (1H), 6,22 (1H), 6,96-7,09 (2H), 7,21-7,44 (6H), 7,56 (1H), 7,61-7,75 (4H), 8,56 (1H) ppm.Analogously to Example 1d, 1.16 g (1.34 mmol) of the compound shown in Example 1i is reacted and, after workup and purification, 1.12 g (1.18 mmol, 88%) of the title compound is isolated as a colorless oil.
1 H NMR (CDCl 3 ): δ = 0.13 (9H), 0.86-2.52 (39H), 1.08 (9H), 2.01 (3H), 3.32-4.85 (9H), 5.00 (1H), 6.22 (1H), 6.96-7.09 (2H), 7.21-7.44 (6H), 7.56 (1H), 7.61 -7.75 (4H), 8.56 (1H) ppm.

(4S(4R,5S,6S,10E/Z,13S,14E))-4-(13-Hydroxy-5-(tetrahydro-2H-pyran-2-yloxy)- 2,6,10,14-tetramethyl-3-oxo-15-(2-pyridyl)-4-(but-3-in-1-yl)-undec-6-in-2-yl)-2,2- dimethyl-[1,3]dioxan(4S (4R, 5S, 6S, 10E / Z, 13S, 14E)) - 4- (13-Hydroxy-5- (tetrahydro-2H-pyran-2-yloxy) - 2,6,10,14-tetramethyl-3-oxo-15- (2-pyridyl) -4- (but-3-in-1-yl) -undec-6-in-2-yl) -2.2 - dimethyl- [1,3] dioxane

In Analogie zu Beispiel 1e setzt man 1,12 g (1,18 mmol) der nach Beispiel 1j dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 654 mg (1,03 mmol, 87%) der Titelverbindung als farbloses Öl. Das 1H-NMR- Spektrum ist deckungsgleich mit dem unter Beispiel 1h, Variante I beschriebenen.In analogy to Example 1e, 1.12 g (1.18 mmol) of the compound shown in Example 1j is reacted and, after workup and purification, 654 mg (1.03 mmol, 87%) of the title compound is isolated as a colorless oil. The 1 H-NMR spectrum is congruent with that described in Example 1h, variant I.

Beispiel 1kExample 1k (3S,6R,7S,8S,12E/Z,15S,16E)-1,3,7,15-Tetrahydroxy-4,4,8,12,16-pentamethyl- 17-(2-pyridyl)-6-(but-3-in-1-yl)-heptadeca-12,16-dien-5-on(3S, 6R, 7S, 8S, 12E / Z, 15S, 16E) -1,3,7,15-tetrahydroxy-4,4,8,12,16-pentamethyl- 17- (2-pyridyl) -6- (but-3-yn-1-yl) -heptadeca-12,16-dien-5-one

Die Lösung von 654 mg (1,03 mmol) der nach Beispiel 1h dargestellten Verbindung in 27 ml wasserfreiem Ethanol versetzt man unter einer Atmosphäre aus trockenem Argon mit 588 mg p-Toluolsulfonsäure-Monohydrat und rührt 3 Stunden bei 23°C. Nach Lösungsmittelabzug chromatographiert man den Rückstand an feinem Kieselgel mit einem Gemisch aus n-Hexan und Ethylacetat. Isoliert werden 484 mg (942 µmol, 91%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = 0,90+0,92 (3H), 1,07 (3H), 1,11-2,16 (14H), 1,29 (3H), 1,63+1,42 (3H), 2,00+2,02 (3H), 2,20-2,60 (4H), 2,98 (1H), 3,48-3,67 (2H), 3,78-3,93 (2H), 4,06-4,23 (3H), 5,16+5,24 (1H), 6,52+6,57 (1H), 7,11 (1H), 7,30 (1H), 7,66 (1H), 8,58 (1H) ppm.The solution of 654 mg (1.03 mmol) of the compound shown in Example 1h in 27 ml of anhydrous ethanol is mixed with 588 mg of p-toluenesulfonic acid monohydrate under an atmosphere of dry argon and stirred at 23 ° C. for 3 hours. After removal of the solvent, the residue is chromatographed on fine silica gel with a mixture of n-hexane and ethyl acetate. 484 mg (942 µmol, 91%) of the title compound are isolated as a colorless oil.
1 H NMR (CDCl 3 ): δ = 0.90 + 0.92 (3H), 1.07 (3H), 1.11-2.16 (14H), 1.29 (3H), 1.63 +1.42 (3H), 2.00 + 2.02 (3H), 2.20-2.60 (4H), 2.98 (1H), 3.48-3.67 (2H), 3, 78-3.93 (2H), 4.06-4.23 (3H), 5.16 + 5.24 (1H), 6.52 + 6.57 (1H), 7.11 (1H), 7 , 30 (1H), 7.66 (1H), 8.58 (1H) ppm.

Beispiel 1lExample 1l (3S,6R,7S,8S,12E/Z,15S,16E)-1,3,7,15-Tetrakis-[[dimethyl(1,1- dimethylethyl)silyl]oxy]-4,4,8,12,16-pentamethyl-17-(2-pyridyl)-6-(but-3-in-1-yl)- heptadeca-12,16-dien-5-on(3S, 6R, 7S, 8S, 12E / Z, 15S, 16E) -1,3,7,15-tetrakis - [[dimethyl (1,1- dimethylethyl) silyl] oxy] -4,4,8,12,16-pentamethyl-17- (2-pyridyl) -6- (but-3-yn-1-yl) - heptadeca-12,16-dien-5-one

Die Lösung von 673 mg (1,31 mmol) der nach Beispiel 1k dargestellten Verbindung in 37 ml wasserfreiem Dichlormethan kühlt man unter einer Atmosphäre aus trockenem Argon auf -78°C, versetzt mit 2,14 ml 2,6-Lutidin, 2,41 ml Trifluormethansulfonsäure-tert.-butyldimethylsilylester, läßt innerhalb von 2 Stunden auf 0°C erwärmen und rührt noch 2 Stunden. Man gießt in gesättigte Natriumhydrogencarbonatlösung und extrahiert mehrfach mit Dichlormethan. Die vereinigten organischen Extrakte trocknet man über Natriumsulfat und engt im Vakuum ein. Nach Säulenchromatographie an Kieselgel mit einem Gradientensystem aus n-Hexan und Ethylacetat isoliert man 1,11 g (1,29 mmol, 99%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = -0,01-0,12 (24H), 0,82-2,33 (55H), 1,08 (3H), 1,22 (3H), 1,60+1,68 (3H), 2,05 (3H), 3,22 (1H), 3,51-3,73 (2H), 3,81 (1H), 3,92 (1H), 4,11 (1H), 5,18 (1H), 6,47 (1H), 7,08 (1H), 7,22 (1H), 7,61 (1H), 8,59 (1H) ppm.The solution of 673 mg (1.31 mmol) of the compound shown in Example 1k in 37 ml of anhydrous dichloromethane is cooled to -78 ° C. under an atmosphere of dry argon, mixed with 2.14 ml of 2,6-lutidine, 2 41 ml of tert-butyldimethylsilyl trifluoromethanesulfonate, allow to warm to 0 ° C. within 2 hours and stir for a further 2 hours. It is poured into saturated sodium bicarbonate solution and extracted several times with dichloromethane. The combined organic extracts are dried over sodium sulfate and concentrated in vacuo. After column chromatography on silica gel with a gradient system of n-hexane and ethyl acetate, 1.11 g (1.29 mmol, 99%) of the title compound is isolated as a colorless oil.
1 H-NMR (CDCl 3 ): δ = -0.01-0.12 (24H), 0.82-2.33 (55H), 1.08 (3H), 1.22 (3H), 1, 60 + 1.68 (3H), 2.05 (3H), 3.22 (1H), 3.51-3.73 (2H), 3.81 (1H), 3.92 (1H), 4, 11 (1H), 5.18 (1H), 6.47 (1H), 7.08 (1H), 7.22 (1H), 7.61 (1H), 8.59 (1H) ppm.

Beispiel 1mExample 1m (3S,6R,7S,8S,12E/Z,15S,16E)-1-Hydroxy-3,7,15-tris-[[dimethyl(1,1- dimethylethyl)silyl]oxy]-4,4,8,12,16-pentamethyl-17-(2-pyridyl)-6-(but-3-in-1-yl)- heptadeca-12,16-dien-5-on(3S, 6R, 7S, 8S, 12E / Z, 15S, 16E) -1-hydroxy-3,7,15-tris - [[dimethyl (1,1- dimethylethyl) silyl] oxy] -4,4,8,12,16-pentamethyl-17- (2-pyridyl) -6- (but-3-yn-1-yl) - heptadeca-12,16-dien-5-one

Die Lösung von 1,10 mg (1,13 mmol) der nach Beispiel 1l dargestellten Verbindung in einem Gemisch aus 14 ml Dichlormethan und 14 ml Methanol versetzt man bei 23°C unter einer Atmosphäre aus trockenem Argon mit 312 mg Campher-10-sulfonsäure und rührt 2 Stunden. Man gießt in eine gesättigte Natriumhydrogencarbonatlösung und extrahiert mehrfach mit Dichlormethan. Die vereinigten organischen Extrakte trocknet man über Natriumsulfat und engt im Vakuum ein. Nach Säulenchromatographie an feinem Kieselgel mit einem Gradientensystem aus n-Hexan und Ethylacetat isoliert man 814 mg (950 µmol, 84%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = 0,01-0,13 (18H), 0,83-2,33 (47H), 1,12 (3H), 1,23 (3H), 1,61+1,68 (3H), 2,05 (3H), 3,28 (1H), 3,68 (2H), 3,84 (1H), 4,02-4,18 (2H), 5,18 (1H), 6,48 (1H), 7,08 (1H), 7,22 (1H), 7,61 (1H), 8,60 (1H) ppm.The solution of 1.10 mg (1.13 mmol) of the compound shown in Example 1l in a mixture of 14 ml of dichloromethane and 14 ml of methanol is mixed with 232 mg of camphor-10-sulfonic acid at 23 ° C. under an atmosphere of dry argon and stir for 2 hours. It is poured into a saturated sodium hydrogen carbonate solution and extracted several times with dichloromethane. The combined organic extracts are dried over sodium sulfate and concentrated in vacuo. After column chromatography on fine silica gel with a gradient system of n-hexane and ethyl acetate, 814 mg (950 µmol, 84%) of the title compound is isolated as a colorless oil.
1 H NMR (CDCl 3 ): δ = 0.01-0.13 (18H), 0.83-2.33 (47H), 1.12 (3H), 1.23 (3H), 1.61 +1.68 (3H), 2.05 (3H), 3.28 (1H), 3.68 (2H), 3.84 (1H), 4.02-4.18 (2H), 5.18 (1H), 6.48 (1H), 7.08 (1H), 7.22 (1H), 7.61 (1H), 8.60 (1H) ppm.

Beispiel 1nExample 1n (3S,6R,7S,8S,12E/Z,15S,16E)-3,7,15-Tris-[[dimethyl(1,1-dimethylethyl)silyl]oxy]- 4,4,8,12,16-pentamethyl-5-oxo-17-(2-pyridyl)-6-(but-3-in-1-yl)-heptadeca-12,16- dienal(3S, 6R, 7S, 8S, 12E / Z, 15S, 16E) -3,7,15-tris - [[dimethyl (1,1-dimethylethyl) silyl] oxy] - 4,4,8,12,16-pentamethyl-5-oxo-17- (2-pyridyl) -6- (but-3-in-1-yl) -heptadeca-12.16- dienal

Die Lösung von 0,129 ml Oxalylchlorid in 6,3 ml wasserfreiem Dichlormethan kühlt man unter einer Atmosphäre aus trockenem Argon auf -70°C, versetzt mit 209 µl Dimethylsulfoxid, der Lösung von 814 mg (950 µmol) der nach Beispiel 1m dargestellten Verbindung in 6,3 ml wasserfreiem Dichlormethan und rührt 0,5 Stunden. Anschließend versetzt man mit 646 µl Triethylamin, läßt 1 Stunde bei -30°C reagieren und versetzt mit n-Hexan und gesättigter Natriumhydrogencarbonatlösung. Die organische Phase wird abgetrennt, die wässrige noch mehrfach mit n-Hexan extrahiert, die vereinigten organischen Extrakte mit Wasser gewaschen und über Magnesiumsulfat getrocknet. Den nach Filtration und Lösungsmittelabzug erhaltenen Rückstand setzt man ohne Reinigung weiter um.The solution of 0.129 ml oxalyl chloride in 6.3 ml anhydrous dichloromethane cooled to -70 ° C under an atmosphere of dry argon, mixed with 209 µl of dimethyl sulfoxide, the solution of 814 mg (950 µmol) according to the example 1m compound shown in 6.3 ml of anhydrous dichloromethane and stirred 0.5 hours. 646 μl of triethylamine are then added and the mixture is left for 1 hour react at -30 ° C and mixed with n-hexane and saturated Sodium bicarbonate solution. The organic phase is separated off aqueous extracted several times with n-hexane, the combined organic Extracts washed with water and dried over magnesium sulfate. The after filtration and removal of solvent residue is used without Cleaning continues around.

Beispiel 1oExample 1o (3S,6R,7S,8S,12Z,15S,16E)-3,7,15-Tris-[[dimethyl(1,1-dimethylethyl)silyl]oxy]- 4,4,8,12,16-pentamethyl-5-oxo-17-(2-pyridyl)-6-(but-3-in-1-yl)-heptadeca-12,16- diensäure (A) und (3S,6R,7S,8S,12E,15S,16E)-3,7,15-Tris-[[dimethyl(1,1- dimethylethyl)silyl]oxy]-4,4,8,12,16-pentamethyl-5-oxo-17-(2-pyridyl)-6-(but-3-in- 1-yl)-heptadeca-12,16-diensäure (B)(3S, 6R, 7S, 8S, 12Z, 15S, 16E) -3,7,15-tris - [[dimethyl (1,1-dimethylethyl) silyl] oxy] - 4,4,8,12,16-pentamethyl-5-oxo-17- (2-pyridyl) -6- (but-3-in-1-yl) -heptadeca-12.16- dienoic acid (A) and (3S, 6R, 7S, 8S, 12E, 15S, 16E) -3,7,15-tris - [[dimethyl (1,1- dimethylethyl) silyl] oxy] -4,4,8,12,16-pentamethyl-5-oxo-17- (2-pyridyl) -6- (but-3-in 1-yl) -heptadeca-12,16-dienoic acid (B)

Die Lösung von 852 mg (max. 950 µmol) der nach Beispiel 1n dargestellten Verbindung in 23 ml Aceton kühlt man auf -30°C, versetzt mit 1,19 ml einer standardisierten, 8 N Chromschwefelsäurelösung und rührt 1 Stunde. Man gießt in ein Gemisch aus Wasser und Diethylether, wäscht die organische Phase mit gesättigter Natriumchloridlösung und trocknet über Natriumsulfat. Nach Filtration und Lösungsmittelabzug reinigt man den Rückstand durch Chromatographie an feinem Kieselgel mit einem Gradientensystem aus n-Hexan und Ethylacetat. Isoliert werden 298 mg (342 µmol, 36% bezogen auf Edukt in Beispiel 1l) der Titelverbindung A sowie 234 mg (269 µmol, 28% bezogen auf Edukt in Beispiel 1l) der Titelverbindung B jeweils als farbloses Öl.
1H-NMR (CDCl3) von A: δ = -0,02-0,15 (18H), 0,81-0,99 (30H), 1,05-2,3 (15H), 1,12 (3H), 1,24 (3H), 1,71 (3H), 1,92 (3H), 2,38 (1H), 2,51 (1H), 3,27 (1H), 3,80 (1H), 4,17 (1H), 4,43 (1H), 5,23 (1H), 6,67 (1H), 7,18 (1H), 7,36 (1H), 7,72 (1H), 8,62 (1H) ppm.
1H-NMR (CDCl3) von B: δ = -0,01-0,19 (18H), 0,80-0,96 (30H), 1,00-2,45 (16H), 1,13 (3H), 1,27 (3H), 1,57 (3H), 1,94 (3H), 2,54 (1H), 3,28 (1H), 3,88 (1H), 4,13 (1H), 4,40 (1H), 5,12 (1H), 6,49 (1H), 7,18 (1H), 7,38 (1H), 7,71 (1H), 8,62 (1H) ppm.The solution of 852 mg (max. 950 μmol) of the compound shown in Example 1n in 23 ml of acetone is cooled to -30 ° C., 1.19 ml of a standardized 8N chromosulfuric acid solution are added and the mixture is stirred for 1 hour. It is poured into a mixture of water and diethyl ether, the organic phase is washed with saturated sodium chloride solution and dried over sodium sulfate. After filtration and removal of the solvent, the residue is purified by chromatography on fine silica gel using a gradient system composed of n-hexane and ethyl acetate. 298 mg (342 μmol, 36% based on starting material in Example 1l) of the title compound A and 234 mg (269 µmol, 28% based on starting material in Example 1l) of the title compound B are each isolated as a colorless oil.
1 H NMR (CDCl 3 ) of A: δ = -0.02-0.15 (18H), 0.81-0.99 (30H), 1.05-2.3 (15H), 1.12 (3H), 1.24 (3H), 1.71 (3H), 1.92 (3H), 2.38 (1H), 2.51 (1H), 3.27 (1H), 3.80 ( 1H), 4.17 (1H), 4.43 (1H), 5.23 (1H), 6.67 (1H), 7.18 (1H), 7.36 (1H), 7.72 (1H ), 8.62 (1H) ppm.
1 H NMR (CDCl 3 ) of B: δ = -0.01-0.19 (18H), 0.80-0.96 (30H), 1.00-2.45 (16H), 1.13 (3H), 1.27 (3H), 1.57 (3H), 1.94 (3H), 2.54 (1H), 3.28 (1H), 3.88 (1H), 4.13 ( 1H), 4.40 (1H), 5.12 (1H), 6.49 (1H), 7.18 (1H), 7.38 (1H), 7.71 (1H), 8.62 (1H) ) ppm.

Beispiel 1pExample 1p (3S,6R,7S,8S,12Z,15S,16E)-15-Hydroxy-3,7-bis-[[dimethyl(1,1- dimethylethyl)silyl]oxy]-4,4,8,12,16-pentamethyl-5-oxo-17-(2-pyridyl)-6-(but-3-in- 1-yl)-heptadeca-12,16-diensäure(3S, 6R, 7S, 8S, 12Z, 15S, 16E) -15-hydroxy-3,7-bis - [[dimethyl (1,1- dimethylethyl) silyl] oxy] -4,4,8,12,16-pentamethyl-5-oxo-17- (2-pyridyl) -6- (but-3-in 1-yl) -heptadeca-12,16-dienoic acid

In Analogie zu Beispiel 1e setzt man 298 mg (342 µmol) der nach Beispiel 1o dargestellten Verbindung A um und isoliert nach Aufarbeitung 294 mg (max. 342 µmol) der Titelverbindung als Rohprodukt, das man ohne Reinigung weiter umsetzt. Analogously to Example 1e, 298 mg (342 µmol) of that according to Example 10 are used Compound A shown and isolated after working up 294 mg (max. 342 µmol) the title compound as a crude product that you can continue without purification implements.  

Beispiel 1qExample 1q (4S,7R,8S,9S,13Z,16S(E))-4,8-Bis-[[dimethyl(1,1-dimethylethyl)silyl]oxy]-16-(1- methyl-2-(2-pyridyl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)- cyclohexadec-13-en-2,6-dion(4S, 7R, 8S, 9S, 13Z, 16S (E)) - 4,8-bis - [[dimethyl (1,1-dimethylethyl) silyl] oxy] -16- (1- methyl-2- (2-pyridyl) ethenyl) -1-oxa-5,5,9,13-tetramethyl-7- (but-3-in-1-yl) - cyclohexadec-13-en-2,6-dione

Die Lösung von 294 mg (max. 342 µmol) der nach Beispiel 1p dargestellten Verbindung in einem Gemisch aus 2,6 ml wasserfreiem Tetrahydrofuran und 30 ml Toluol versetzt man unter einer Atmosphäre aus trockenem Argon mit 284 µl Triethylamin, 268 µl 2,4,6-Trichlorbenzoylchlorid und rührt 20 Minuten. Man tropft diese Lösung innerhalb von 4,5 Stunden zu der Lösung von 434 mg 4- Dimethylaminopyridin in 132 ml Toluol und rührt 0,5 Stunden bei 23°C nach. Man engt ein, nimmt ein wenig Dichlormethan auf und reinigt durch Chromatographie an feinem Kieselgel mit einem Gradientensystem aus n- Hexan und Ethylacetat. Isoliert werden 136 mg (184 µmol, 54%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = -0,08 (3H), 0,13 (9H), 0,80-2,32 (12H), 0,85 (9H), 0,94 (9H), 0,99 (3H), 1,15 (3H), 1,24 (3H), 1,68 (3H), 2,13 (3H), 2,47 (1H), 2,59-2,89 (3H), 3,11 (1H), 4,00 (1H), 4,06 (1H), 5,00 (1H), 5,18 (1H), 6,57 (1H), 7,10 (1H), 7,26 (1H), 7,63 (1H), 8,60 (1H) ppm.The solution of 294 mg (max. 342 μmol) of the compound shown in Example 1p in a mixture of 2.6 ml of anhydrous tetrahydrofuran and 30 ml of toluene is mixed with 284 μl of triethylamine, 268 μl of 2.4, under an atmosphere of dry argon. 6-trichlorobenzoyl chloride and stirred for 20 minutes. This solution is added dropwise to the solution of 434 mg of 4-dimethylaminopyridine in 132 ml of toluene in the course of 4.5 hours and the mixture is stirred at 23 ° C. for 0.5 hour. The mixture is concentrated, a little dichloromethane is taken up and the mixture is purified by chromatography on fine silica gel using a gradient system composed of n-hexane and ethyl acetate. 136 mg (184 μmol, 54%) of the title compound are isolated as a colorless oil.
1 H NMR (CDCl 3 ): δ = -0.08 (3H), 0.13 (9H), 0.80-2.32 (12H), 0.85 (9H), 0.94 (9H) , 0.99 (3H), 1.15 (3H), 1.24 (3H), 1.68 (3H), 2.13 (3H), 2.47 (1H), 2.59-2.89 (3H), 3.11 (1H), 4.00 (1H), 4.06 (1H), 5.00 (1H), 5.18 (1H), 6.57 (1H), 7.10 ( 1H), 7.26 (1H), 7.63 (1H), 8.60 (1H) ppm.

Beispiel 1example 1 (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion(4S, 7R, 8S, 9S, 13Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) -1- oxa-5,5,9,13-tetramethyl-7- (but-3-in-1-yl) -cyclohexadec-13-en-2,6-dione

Die Lösung von 20 mg (27 µmol) der nach Beispiel 1p dargestellten Verbindung in 2 ml wasserfreiem Tetrahydrofuran versetzt man unter einer Atmosphäre aus trockenem Argon portionsweise mit insgesamt 0,57 ml HF-Pyridin-Komplex und rührt bei 23°C 24 Stunden. Man gießt in gesättigte Natriumhydrogencarbonatlösung, extrahiert mehrfach mit Dichlormethan und trocknet die vereinigten organischen Extrakte über Natriumsulfat. Nach Filtration und Lösungsmittelabzug reinigt man den erhaltenen Rückstand durch Chromatographie an feinem Kieselgel mit einem Gemisch aus n-Hexan und Ethylacetat. Isoliert werden 9,1 mg (17,9 µmol, 66%) der Titelverbindung als farbloses Öl sowie mg Monosilylether.
1H-NMR (CDCl3): δ = 1,09 (6H), 1,19-2,12 (11H), 1,38 (3H), 6,9 (3H), 2,06 (3H), 2,21-2,41 (3H), 2,50 (1H), 2,63 (1H), 2,68 (1H), 3,53 (1H), 3,70 (1H), 4,42 (1H), 4,59 (1H), 5,12 (1H), 5,22 (1H), 6,61 (1H), 7,13 (1H), 7,29 (1H), 7,68 (1H), 8,53 (1H) ppm.The solution of 20 mg (27 μmol) of the compound shown in Example 1p in 2 ml of anhydrous tetrahydrofuran is added in portions under a dry argon atmosphere with a total of 0.57 ml of HF-pyridine complex and stirred at 23 ° C. for 24 hours. It is poured into saturated sodium bicarbonate solution, extracted several times with dichloromethane and the combined organic extracts are dried over sodium sulfate. After filtration and removal of the solvent, the residue obtained is purified by chromatography on fine silica gel with a mixture of n-hexane and ethyl acetate. 9.1 mg (17.9 µmol, 66%) of the title compound are isolated as a colorless oil and mg monosilyl ether.
1 H-NMR (CDCl 3 ): δ = 1.09 (6H), 1.19-2.12 (11H), 1.38 (3H), 6.9 (3H), 2.06 (3H), 2.21-2.41 (3H), 2.50 (1H), 2.63 (1H), 2.68 (1H), 3.53 (1H), 3.70 (1H), 4.42 ( 1H), 4.59 (1H), 5.12 (1H), 5.22 (1H), 6.61 (1H), 7.13 (1H), 7.29 (1H), 7.68 (1H ), 8.53 (1H) ppm.

Beispiel 2Example 2 (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6-dion(4S, 7R, 8S, 9S, 13Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) -1- oxa-5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione Beispiel 2aExample 2a (4S,7R,8S,9S,13Z,16S(E))-4,8-Bis-[[dimethyl(1,1-dimethylethyl)silyl]oxy]-16-(1- methyl-2-(2-pyridyl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)- cyclohexadec-13-en-2,6-dion(4S, 7R, 8S, 9S, 13Z, 16S (E)) - 4,8-bis - [[dimethyl (1,1-dimethylethyl) silyl] oxy] -16- (1- methyl-2- (2-pyridyl) ethenyl) -1-oxa-5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) - cyclohexadec-13-en-2,6-dione

Die Lösung von 25 mg (34 µmol) der nach Beispiel 1q dargestellten Verbindung in 3 ml Ethanol versetzt man mit 25 µl Pyridin, einer katalytischen Menge von Palladium auf Bariumsulfat (10%ig) und hydriert unter 1 Atmosphäre Wasserstoff. Nach Filtration und Lösungsmittelabzug reinigt man den Rückstand durch Chromatographie an einer analytischen Dünnschichtplatte. Als Laumittel dient ein Gemisch aus n-Hexan und Ethylacetat. Isoliert werden 13 mg (18 µmol, 52%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = -0,10 (3H), 0,06 (3H), 0,11 (6H), 0,80-2,20 (11H), 0,83 (9H), 0,92 (9H), 0,98 (3H), 1,12 (3H), 1,19 (3H), 1,67 (3H), 2,12 (3H), 2,43 (1H), 2,55-2,82 (3H), 3,07 (1H), 4,00 (1H), 4,03 (1H), 4,90-5,03 (3H), 5,18 (1H), 5,72 (1H), 6,57 (1H), 7,09 (1H), 7,25 (1H), 7,62 (1H), 8,59 (1H) ppm.The solution of 25 mg (34 μmol) of the compound shown in Example 1q in 3 ml of ethanol is mixed with 25 μl of pyridine, a catalytic amount of palladium on barium sulfate (10%) and hydrogenated under 1 atmosphere of hydrogen. After filtration and removal of solvent, the residue is purified by chromatography on an analytical thin-layer plate. A mixture of n-hexane and ethyl acetate is used as the de-icing agent. 13 mg (18 µmol, 52%) of the title compound are isolated as a colorless oil.
1 H NMR (CDCl 3 ): δ = -0.10 (3H), 0.06 (3H), 0.11 (6H), 0.80-2.20 (11H), 0.83 (9H) , 0.92 (9H), 0.98 (3H), 1.12 (3H), 1.19 (3H), 1.67 (3H), 2.12 (3H), 2.43 (1H), 2.55-2.82 (3H), 3.07 (1H), 4.00 (1H), 4.03 (1H), 4.90-5.03 (3H), 5.18 (1H), 5.72 (1H), 6.57 (1H), 7.09 (1H), 7.25 (1H), 7.62 (1H), 8.59 (1H) ppm.

Beispiel 2Example 2 (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6-dion(4S, 7R, 8S, 9S, 13Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) -1- oxa-5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione

In Analogie zu Beispiel 1 setzt man 10,3 mg (14 µmol) der nach Beispiel 2a dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 5,7 mg (11 µmol, 80%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = 1,04 (3H), 1,09 (3H), 0,25-2,38 (13H), 1,36 (3H), 1,70 (3H), 2,07 (3H), 2,48 (1H), 2,63 (1H), 2,74 (1H), 3,31 (1H), 3,69 (1H), 4,38 (1H), 4,61 (1H), 4,97 (1H), 5,02 (1H), 5,11 (1H), 5,19 (1H), 5,77 (1H), 6,60 (1H), 7,13 (1H), 7,29 (1H), 7,68 (1H), 8,54 (1H) ppm.Analogously to Example 1, 10.3 mg (14 μmol) of the compound shown in Example 2a is reacted and, after workup and purification, 5.7 mg (11 μmol, 80%) of the title compound is isolated as a colorless oil.
1 H-NMR (CDCl 3 ): δ = 1.04 (3H), 1.09 (3H), 0.25-2.38 (13H), 1.36 (3H), 1.70 (3H), 2.07 (3H), 2.48 (1H), 2.63 (1H), 2.74 (1H), 3.31 (1H), 3.69 (1H), 4.38 (1H), 4 , 61 (1H), 4.97 (1H), 5.02 (1H), 5.11 (1H), 5.19 (1H), 5.77 (1H), 6.60 (1H), 7, 13 (1H), 7.29 (1H), 7.68 (1H), 8.54 (1H) ppm.

(4S,7R,8S,9S,13E,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6-dion(4S, 7R, 8S, 9S, 13E, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) -1- oxa-5,5,9,13-tetramethyl-7- (prop-2-in-1-yl) cyclohexadec-13-ene-2,6-dione Beispiel 3aExample 3a (3S,6R,7S,8S,12E,15S,16E)-15-Hydroxy-3,7-bis-[[dimethyl(1,1- dimethylethyl)silyl]oxy]-4,4,8,12,16-pentamethyl-5-oxo-17-(2-pyridyl)-6-(prop-2- in-1-yl)-heptadeca-12,16-diensäure(3S, 6R, 7S, 8S, 12E, 15S, 16E) -15-hydroxy-3,7-bis - [[dimethyl (1,1- dimethylethyl) silyl] oxy] -4,4,8,12,16-pentamethyl-5-oxo-17- (2-pyridyl) -6- (prop-2- in-1-yl) -heptadeca-12,16-dienoic acid

In Analogie zu Beispiel 1e setzt man 234 mg (269 µmol) der nach Beispiel 1o dargestellten Verbindung B um und isoliert nach Aufarbeitung 229 mg (max. 269 µmol) der Titelverbindung als Rohprodukt, das man ohne Reinigung weiter umsetzt.Analogously to Example 1e, 234 mg (269 µmol) of that according to Example 10 are used Compound B shown and isolated after working up 229 mg (max. 269 µmol) the title compound as a crude product that you can continue without purification implements.

Beispiel 3bExample 3b (4S,7R,8S,9S,13E,16S(E))-4,8-Bis-[[dimethyl(1,1-dimethylethyl)silyl]oxy]-16-(1- methyl-2-(2-pyridyl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)- cyclohexadec-13-en-2,6-dion(4S, 7R, 8S, 9S, 13E, 16S (E)) - 4,8-bis - [[dimethyl (1,1-dimethylethyl) silyl] oxy] -16- (1- methyl-2- (2-pyridyl) ethenyl) -1-oxa-5,5,9,13-tetramethyl-7- (prop-2-in-1-yl) - cyclohexadec-13-en-2,6-dione

In Analogie zu Beispiel 1q setzt man 229 mg (max. 269 µmol) der nach Beispiel 3a dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 112 mg (152 µmol, 56%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = 0,05 (3H), 0,11 (6H), 0,15 (3H), 0,80-2,30 (33H), 1,13 (3H), 1,21 (3H), 1,62 (3H), 2,16 (3H), 2,40-2,72 (4H), 3,10 (1H), 3,91 (1H), 4,46 (1H), 5,22 (1H), 5,30 (1H), 6,56 (1H), 7,09 (1H), 7,20 (1H), 7,62 (1H), 8,60 (1H) ppm.Analogously to Example 1q, 229 mg (max. 269 µmol) of the compound shown in Example 3a are reacted and 112 mg (152 µmol, 56%) of the title compound is isolated as a colorless oil after working up and purification.
1 H-NMR (CDCl 3 ): δ = 0.05 (3H), 0.11 (6H), 0.15 (3H), 0.80-2.30 (33H), 1.13 (3H), 1.21 (3H), 1.62 (3H), 2.16 (3H), 2.40-2.72 (4H), 3.10 (1H), 3.91 (1H), 4.46 ( 1H), 5.22 (1H), 5.30 (1H), 6.56 (1H), 7.09 (1H), 7.20 (1H), 7.62 (1H), 8.60 (1H) ) ppm.

Beispiel 3Example 3 (4S,7R,8S,9S,13E,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6-dion(4S, 7R, 8S, 9S, 13E, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) -1- oxa-5,5,9,13-tetramethyl-7- (prop-2-in-1-yl) cyclohexadec-13-ene-2,6-dione

In Analogie zu Beispiel 1 setzt man 72 mg (98 µmol) der nach Beispiel 3b dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 32 mg (63 µmol, 64%) der Titelverbindung als farblosen Schaum.
1H-NMR (CDCl3): δ = 1,00 (3H), 1,04 (3H), 1,30-2,71 (16H), 1,32 (3H), 1,61 (3H), 2,10 (3H), 3,63 (1H), 3,70 (1H), 3,86 (1H), 3,99 (1H), 4,48 (1H), 5,10 (1H), 5,41 (1H), 6,58 (1H), 7,13 (1H), 7,33 (1H), 7,68 (1H), 8,54 (1H) ppm.Analogously to Example 1, 72 mg (98 μmol) of the compound shown in Example 3b are reacted and, after workup and purification, 32 mg (63 μmol, 64%) of the title compound are isolated as a colorless foam.
1 H-NMR (CDCl 3 ): δ = 1.00 (3H), 1.04 (3H), 1.30-2.71 (16H), 1.32 (3H), 1.61 (3H), 2.10 (3H), 3.63 (1H), 3.70 (1H), 3.86 (1H), 3.99 (1H), 4.48 (1H), 5.10 (1H), 5 , 41 (1H), 6.58 (1H), 7.13 (1H), 7.33 (1H), 7.68 (1H), 8.54 (1H) ppm.

Beispiel 4Example 4 (1S,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion (A) und (1R,3S(E),7S,10R,11S,12S,16S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion (B)(1S, 3S (E), 7S, 10R, 11S, 12S, 16R) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- methyl-2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17- dioxabicyclo [14.1.0] heptadecane-5,9-dione (A) and (1R, 3S (E), 7S, 10R, 11S, 12S, 16S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- methyl-2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17- dioxabicyclo [14.1.0] heptadecane-5,9-dione (B)

Die Lösung von 5 mg (10 µmol) der nach Beispiel 1 dargestellten Verbindung in 1 ml Dichlormethan versetzt man unter einer Atmospäre aus trockenem Argon bei -20°C mit 11,3 µl einer 20%igen Lösung von Trifluoessigsäure in Dichlormethan und 5,6 mg m-Chlorperbenxoesäure (60%ig). Man rührt 18 Stunden bei -18°C, gießt auf gesättigte Natriumthiosulfatlösung, extrahiert mehrfach mit Dichlormethan, wäscht die vereinigten organischen Extrakte mit Natriumhydrogencarbonatlösung, gesättigter Natriumchloridlösung und trocknet über Magnesiumsulfat. Den nach Filtration und Lösungsmittelabzug erhaltenen Rückstand reinigt man durch Chromatographie an einer analytischen Dünnschichtplatte. Als Lauf- und Elutionsmittel dient ein Gemisch aus Dichlormethan und Ethanol. Isoliert werden 1,3 mg (2,5 µmol, 25%) der Titelverbindung A (oder B) sowie 2,0 mg (3,8 µmol, 39%) der Titelverbindung B (oder A) jeweils als farbloses Öl.
1H-NMR (CDCl3) von A (oder B): δ = 1,01 (3H), 1,07 (3H), 1,23-2,20 (13H), 1,30 (3H), 1,46 (3H), 2,10 (3H), 2,26 (1H), 2,40 (1H), 2,58 (1H), 2,82 (1H), 2,97 (1H), 3,63 (2H), 4,39 (1H), 5,22 (1H), 5,47 (1H), 6,61 (1H), 7,15 (1H), 7,28 (1H), 7,69 (1H), 8,55 (1H) ppm.
1H-NMR (CDCl3) von B (oder A): δ = 0,98 (3H), 1,08 (3H), 1,27-2,19 (13H), 1,32 (3H), 1,43 (3H), 2,12 (3H), 2,30 (1H), 2,48 (1H), 2,70 (1H), 2,96 (1H), 3,15 (1H), 3,47 (1H), 3,57 (1H), 4,01 (1H), 4,49 (1H), 5,50 (1H), 6,67 (1H), 7,12 (1H), 7,27 (1H), 7,66 (1H), 8,58 (1H) ppm.The solution of 5 mg (10 μmol) of the compound shown in Example 1 in 1 ml of dichloromethane is mixed under an atmosphere of dry argon at -20 ° C. with 11.3 μl of a 20% solution of trifluoroacetic acid in dichloromethane and 5.6 mg m-chloroperbenxic acid (60%). The mixture is stirred at -18 ° C. for 18 hours, poured onto saturated sodium thiosulfate solution, extracted several times with dichloromethane, the combined organic extracts are washed with sodium hydrogen carbonate solution, saturated sodium chloride solution and dried over magnesium sulfate. The residue obtained after filtration and removal of solvent is purified by chromatography on an analytical thin-layer plate. A mixture of dichloromethane and ethanol is used as the eluent and eluent. 1.3 mg (2.5 μmol, 25%) of the title compound A (or B) and 2.0 mg (3.8 μmol, 39%) of the title compound B (or A) are each isolated as a colorless oil.
1 H NMR (CDCl 3 ) of A (or B): δ = 1.01 (3H), 1.07 (3H), 1.23-2.20 (13H), 1.30 (3H), 1 , 46 (3H), 2.10 (3H), 2.26 (1H), 2.40 (1H), 2.58 (1H), 2.82 (1H), 2.97 (1H), 3, 63 (2H), 4.39 (1H), 5.22 (1H), 5.47 (1H), 6.61 (1H), 7.15 (1H), 7.28 (1H), 7.69 (1H), 8.55 (1H) ppm.
1 H NMR (CDCl 3 ) of B (or A): δ = 0.98 (3H), 1.08 (3H), 1.27-2.19 (13H), 1.32 (3H), 1 , 43 (3H), 2.12 (3H), 2.30 (1H), 2.48 (1H), 2.70 (1H), 2.96 (1H), 3.15 (1H), 3, 47 (1H), 3.57 (1H), 4.01 (1H), 4.49 (1H), 5.50 (1H), 6.67 (1H), 7.12 (1H), 7.27 (1H), 7.66 (1H), 8.58 (1H) ppm.

Beispiel 5Example 5 (1S,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion (A) und (1R,3S(E),7S,10R,11S,12S,16S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion (B)(1S, 3S (E), 7S, 10R, 11S, 12S, 16R) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- methyl-2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17- dioxabicyclo [14.1.0] heptadecane-5,9-dione (A) and (1R, 3S (E), 7S, 10R, 11S, 12S, 16S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- methyl-2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17- dioxabicyclo [14.1.0] heptadecane-5,9-dione (B)

In Analogie zu Beispiel 4 setzt man 6,6 mg (13 µmol) der nach Beispiel 2 dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 1,4 mg (2,7 µmol, 20%) der Titelverbindung A (oder B) sowie 0,9 mg (1,7 µmol, 13%) der Titelverbindung B (oder A) jeweils als farblosen Schaum.
1H-NMR (CDCl3) von A (oder B): δ = 1,00 (3H), 1,07 (3H), 1,21-2,05 (12H), 1,30 (3H), 1,40 (3H), 2,10 (3H), 2,16 (1H), 2,38 (1H), 2,57 (1H), 2,81 (1H), 2,97 (1H), 3,44 (1H), 3,63 (1H), 4,38 (1H), 4,98 (1H), 5,02 (1H), 5,28 (1H), 5,45 (1H), 5,77 (1H), 6,62 (1H), 7,18 (1H), 7,31 (1H), 7,71 (1H), 8,56 (1H) ppm.
1H-NMR (CDCl3) von B (oder A): δ = 0,94 (3H), 1,05 (3H), 1,18-2,17 (13H), 1,30 (3H), 1,38 (3H), 2,12 (3H), 2,48 (1H), 2,62 (1H), 2,95 (1H), 3,28 (1H), 3,30 (1H), 3,50 (1H), 3,96 (1H), 4,41 (1H), 4,95 (1H), 5,00 (1H), 5,52 (1H), 5,25 (1H), 6,73 (1H), 7,18 (1H), 7,33 (1H), 7,71 (1H), 8,58 (1H) ppm.Analogously to Example 4, 6.6 mg (13 μmol) of the compound shown in Example 2 are reacted and, after workup and purification, 1.4 mg (2.7 μmol, 20%) of the title compound A (or B) and 0 , 9 mg (1.7 µmol, 13%) of the title compound B (or A) each as a colorless foam.
1 H NMR (CDCl 3 ) of A (or B): δ = 1.00 (3H), 1.07 (3H), 1.21-2.05 (12H), 1.30 (3H), 1 , 40 (3H), 2.10 (3H), 2.16 (1H), 2.38 (1H), 2.57 (1H), 2.81 (1H), 2.97 (1H), 3, 44 (1H), 3.63 (1H), 4.38 (1H), 4.98 (1H), 5.02 (1H), 5.28 (1H), 5.45 (1H), 5.77 (1H), 6.62 (1H), 7.18 (1H), 7.31 (1H), 7.71 (1H), 8.56 (1H) ppm.
1 H NMR (CDCl 3 ) of B (or A): δ = 0.94 (3H), 1.05 (3H), 1.18-2.17 (13H), 1.30 (3H), 1 , 38 (3H), 2.12 (3H), 2.48 (1H), 2.62 (1H), 2.95 (1H), 3.28 (1H), 3.30 (1H), 3, 50 (1H), 3.96 (1H), 4.41 (1H), 4.95 (1H), 5.00 (1H), 5.52 (1H), 5.25 (1H), 6.73 (1H), 7.18 (1H), 7.33 (1H), 7.71 (1H), 8.58 (1H) ppm.

Beispiel 6Example 6 (1S,3S(E),7S,10R,11S,12S,16S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion (A) und (1R,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion (B)(1S, 3S (E), 7S, 10R, 11S, 12S, 16S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- methyl-2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17- dioxabicyclo [14.1.0] heptadecane-5,9-dione (A) and (1R, 3S (E), 7S, 10R, 11S, 12S, 16R) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- methyl-2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17- dioxabicyclo [14.1.0] heptadecane-5,9-dione (B)

In Analogie zu Beispiel 4 setzt man 14 mg (27 µmol) der nach Beispiel 3 dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 7,8 mg (15 µmol, 55%) der Titelverbindung A (oder B) sowie 4,7 mg (9 µmol, 33%) der Titelverbindung B (oder A) jeweils als farblosen Schaum.
1H-NMR (CDCl3) von A (oder B): δ = 0,93 (3H), 1,04 (3H), 1,23-2,19 (13H), 1,29 (3H), 1,42 (3H), 2,13 (3H), 2,28 (1H), 2,48-2,65 (2H), 2,71 (1H), 2,89 (1H), 3,57 (1H), 3,83 (1H), 4,36 (1H), 4,47 (1H), 5,51 (1H), 6,63 (1H), 7,12 (1H), 7,28 (1H), 7,67 (1H), 8,57 (1H) ppm.
1H-NMR (CDCl3) von B (oder A): δ = 0,96 (3H), 1,10 (3H), 1,21-2,18 (13H), 1,26 (3H), 1,40 (3H), 2,10 (3H), 2,29 (1H), 2,61 (2H), 2,86 (1H), 2,99 (1H), 3,58 (1H), 3,79 (2H), 4,37 (1H), 5,46 (1H), 6,61 (1H), 7,12 (1H), 7,26 (1H), 7,66 (1H), 8,57 (1H) ppm.Analogously to Example 4, 14 mg (27 μmol) of the compound shown in Example 3 are reacted and, after workup and purification, 7.8 mg (15 μmol, 55%) of the title compound A (or B) and 4.7 mg ( 9 µmol, 33%) of the title compound B (or A) each as a colorless foam.
1 H NMR (CDCl 3 ) of A (or B): δ = 0.93 (3H), 1.04 (3H), 1.23-2.19 (13H), 1.29 (3H), 1 , 42 (3H), 2.13 (3H), 2.28 (1H), 2.48-2.65 (2H), 2.71 (1H), 2.89 (1H), 3.57 (1H ), 3.83 (1H), 4.36 (1H), 4.47 (1H), 5.51 (1H), 6.63 (1H), 7.12 (1H), 7.28 (1H) , 7.67 (1H), 8.57 (1H) ppm.
1 H NMR (CDCl 3 ) of B (or A): δ = 0.96 (3H), 1.10 (3H), 1.21-2.18 (13H), 1.26 (3H), 1 , 40 (3H), 2.10 (3H), 2.29 (1H), 2.61 (2H), 2.86 (1H), 2.99 (1H), 3.58 (1H), 3, 79 (2H), 4.37 (1H), 5.46 (1H), 6.61 (1H), 7.12 (1H), 7.26 (1H), 7.66 (1H), 8.57 (1H) ppm.

Beispiel 7Example 7 (4S,7R,8S,9S,13E,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6-dion(4S, 7R, 8S, 9S, 13E, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) -1- oxa-5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione

In Analogie zu Beispiel 2a setzt man 14 mg (27 µmol) der nach Beispiel 3 dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 4,1 mg (8 µmol, 29%) der Titelverbindung als farblosen Schaum.
1H-NMR (CDCl3): δ = 0,98 (3H), 1,02 (3H), 1,30 (3H), 1,36-2,68 (16H), 1,61 (3H), 2,09 (3H), 3,43 (1H), 3,70 (1H), 4,17 (1H), 4,45 (1H), 4,94 (1H), 5,00 (1H), 5,09 (1H), 5,39 (1H), 5,72 (1H), 6,58 (1H), 7,12 (1H), 7,35 (1H), 7,67 (1H), 8,52 (1H) ppm.Analogously to Example 2a, 14 mg (27 μmol) of the compound shown in Example 3 are reacted and, after workup and purification, 4.1 mg (8 μmol, 29%) of the title compound is isolated as a colorless foam.
1 H-NMR (CDCl 3 ): δ = 0.98 (3H), 1.02 (3H), 1.30 (3H), 1.36-2.68 (16H), 1.61 (3H), 2.09 (3H), 3.43 (1H), 3.70 (1H), 4.17 (1H), 4.45 (1H), 4.94 (1H), 5.00 (1H), 5 , 09 (1H), 5.39 (1H), 5.72 (1H), 6.58 (1H), 7.12 (1H), 7.35 (1H), 7.67 (1H), 8, 52 (1H) ppm.

Beispiel 8Example 8 (1S,3S(E),7S,10R,11S,12S,16S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion (A) und (1R,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion (B)(1S, 3S (E), 7S, 10R, 11S, 12S, 16S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- methyl-2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17- dioxabicyclo [14.1.0] heptadecane-5,9-dione (A) and (1R, 3S (E), 7S, 10R, 11S, 12S, 16R) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- methyl-2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17- dioxabicyclo [14.1.0] heptadecane-5,9-dione (B)

In Analogie zu Beispiel 4 setzt man 4,1 mg (8 µmol) der nach Beispiel 7 dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 1,7 mg (3,2 µmol, 40%) der Titelverbindung A (oder B) sowie 0,4 mg (0,8 µmol, 9%) der Titelverbindung B (oder A) jeweils als farblosen Schaum.
1H-NMR (CDCl3) von A (oder B): δ = 0,91 (3H), 1,02 (3H), 1,13-2,17 (15H), 1,28 (3H), 1,38 (3H), 2,11 (3H), 2,53 (2H), 2,87 (1H), 2,96 (1H), 3,38 (1H), 3,78 (1H), 4,35 (1H), 4,37 (1H), 4,95 (1H), 5,00 (1H), 5,50 (1H), 5,76 (1H), 6,64 (1H), 7,12 (1H), 7,30 (1H), 7,67 (1H), 8,57 (1H) ppm.
1H-NMR (CDCl3) von B (oder A): δ = 0,92 (3H), 1,09 (3H), 1,18-2,13 (15H), 1,26 (3H), 1,38 (3H), 2,08 (3H), 2,49-2,60 (2H), 2,85-2,99 (2H), 3,39 (1H), 3,72 (1H), 3,89 (1H), 4,28 (1H), 4,92-5,06 (2H), 5,45 (1H), 5,76 (1H), 6,60 (1H), 7,12 (1H), 7,26 (1H), 7,68 (1H), 8,57 (1H) ppm.Analogously to Example 4, 4.1 mg (8 μmol) of the compound shown in Example 7 is reacted and, after workup and purification, 1.7 mg (3.2 μmol, 40%) of the title compound A (or B) and 0 , 4 mg (0.8 µmol, 9%) of the title compound B (or A) each as a colorless foam.
1 H NMR (CDCl 3 ) of A (or B): δ = 0.91 (3H), 1.02 (3H), 1.13-2.17 (15H), 1.28 (3H), 1 , 38 (3H), 2.11 (3H), 2.53 (2H), 2.87 (1H), 2.96 (1H), 3.38 (1H), 3.78 (1H), 4, 35 (1H), 4.37 (1H), 4.95 (1H), 5.00 (1H), 5.50 (1H), 5.76 (1H), 6.64 (1H), 7.12 (1H), 7.30 (1H), 7.67 (1H), 8.57 (1H) ppm.
1 H NMR (CDCl 3 ) of B (or A): δ = 0.92 (3H), 1.09 (3H), 1.18-2.13 (15H), 1.26 (3H), 1 , 38 (3H), 2.08 (3H), 2.49-2.60 (2H), 2.85-2.99 (2H), 3.39 (1H), 3.72 (1H), 3 , 89 (1H), 4.28 (1H), 4.92-5.06 (2H), 5.45 (1H), 5.76 (1H), 6.60 (1H), 7.12 (1H ), 7.26 (1H), 7.68 (1H), 8.57 (1H) ppm.

Beispiel 9Example 9 (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-16-(1-methy4-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en- 2,6-dion(4S, 7R, 8S, 9S, 13Z, 16S (E)) - 4,8-Dihydroxy-16- (1-methy4-2- (2-methylthiazol-4- yl) ethenyl) -1-oxa-5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) -cyclohexadec-13-en- 2,6-dione Beispiel 9aExample 9a (3RS,4S)-4-(2-Methyl-3-hydroxy-hept-6-en-2-yl)-2,2-dimethyl-[1,3]dioxan(3RS, 4S) -4- (2-methyl-3-hydroxy-hept-6-en-2-yl) -2,2-dimethyl- [1,3] dioxane

In Analogie zu Beispiel 1a setzt man 5,5 g (30 mmol) (4S)-4-(2-Methyl-1-oxo­ prop-2-yl)-2,2-dimethyl-[1,3]dioxan, das man in Analogie zu den in DE 197 51 200.3 beschriebenen Verfahren hergestellt hat, mit Prop-2-en-1-yl- magnesiumbromid um und isoliert nach Aufarbeitung und Reinigung 3,84 g (15,8 mmol, 53%) der Titelverbindung als farbloses Öl.Analogously to Example 1a, 5.5 g (30 mmol) of (4S) -4- (2-methyl-1-oxo) are used prop-2-yl) -2,2-dimethyl- [1,3] dioxane, which is analogous to that described in DE 197 51 200.3 described process with prop-2-en-1-yl magnesium bromide and isolated after work-up and purification 3.84 g (15.8 mmol, 53%) of the title compound as a colorless oil.

Beispiel 9bExample 9b (4S)-4-(2-Methyl-3-oxo-hept-6-en-2-yl)-2,2-dimethyl-[1,3]dioxan(4S) -4- (2-Methyl-3-oxo-hept-6-en-2-yl) -2,2-dimethyl- [1,3] dioxane

In Analogie zu Beispiel 1b setzt man 3,84 g (15,8 mmol) der nach Beispiel 9a dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 3,0 g (12,5 mmol, 79%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = 1,07 (3H), 1,14 (3H), 1,33 (4H), 1,41 (3H), 1,62 (1H), 2,29 (2H), 2,60 (2H), 3,86 (1H), 3,97 (1H), 4,05 (1H), 4,96 (1H), 5,02 (1H), 5,81 (1H) ppm.In analogy to example 1b, 3.84 g (15.8 mmol) of the compound shown in example 9a is reacted and 3.0 g (12.5 mmol, 79%) of the title compound is isolated as a colorless oil after working up and purification.
1 H NMR (CDCl 3 ): δ = 1.07 (3H), 1.14 (3H), 1.33 (4H), 1.41 (3H), 1.62 (1H), 2.29 ( 2H), 2.60 (2H), 3.86 (1H), 3.97 (1H), 4.05 (1H), 4.96 (1H), 5.02 (1H), 5.81 (1H) ) ppm.

Beispiel 9cExample 9c (4S(4R,5S,6S,10E/Z,13S,14E))-4-(13-[[Dimethyl(1,1-dimethylethyl)silyl]oxy]-5- hydroxy-2,6,10,14-tetramethyl-3-oxo-15-(2-methylthiazol-4-yl)-4-(prop-2-en-1- yl)-pentadec-2-yl)-2,2-dimethyl-[1,3]dioxan (A) und (4S(4S,5R,6S,10E/Z,13S,14E))-4-(13-[[Dimethyl(1,1-dimethylethyl)silyl]oxy]-5- hydroxy-2,6,10,14-tetramethyl-3-oxo-15-(2-methylthiazol-4-yl)-4-(prop-2-en-1- yl)-pentadec-2-yl)-2,2-dimethyl-[1,3]dioxan (B)(4S (4R, 5S, 6S, 10E / Z, 13S, 14E)) - 4- (13 - [[Dimethyl (1,1-dimethylethyl) silyl] oxy] -5- hydroxy-2,6,10,14-tetramethyl-3-oxo-15- (2-methylthiazol-4-yl) -4- (prop-2-en-1- yl) -pentadec-2-yl) -2,2-dimethyl- [1,3] dioxane (A) and (4S (4S, 5R, 6S, 10E / Z, 13S, 14E)) - 4- (13 - [[Dimethyl (1,1-dimethylethyl) silyl] oxy] -5- hydroxy-2,6,10,14-tetramethyl-3-oxo-15- (2-methylthiazol-4-yl) -4- (prop-2-en-1- yl) -pentadec-2-yl) -2,2-dimethyl- [1,3] dioxane (B)

In Analogie zu Beispiel 1c setzt man 2,07 g (8,61 mmol) der nach Beispiel 9b dargestellten Verbindung mit 2,01 g (4,61 mmol) (2S,6E/Z,9S,10E)-2,6,10- Trimethyl-9-[[dimethyl(1,1-dimethylethyl)silyl]oxy]-1-oxo-11-(2-methylthiazol-4- yl)-undeca-6,10-dien, das man in Analogie zu den in DE 197 51 200.3 beschriebenen Verfahren hergestellt hat, um und isoliert nach Aufarbeitung und Reinigung neben Ausgangsmaterial 995 mg (1,47 mmol, 32%) der Titelverbindung A sowie 784 mg (1,16 mmol, 25%) der Titelverbindung B jeweils als farbloses Öl.
1H-NMR (CDCl3) von A: δ = 0,01 (3H), 0,07 (3H), 0,85 (3H), 0,90 (9H), 0,98 (3H), 1,00-2,33 (12H), 1,23 (3H), 1,33 (3H), 1,39 (3H), 1,60+1,67 (3H), 2,00 (3H), 2,46 (1H), 2,72 (3H), 2,99 (1H), 3,34 (1H), 3,49 (1H), 3,87 (1H), 3,98 (1H), 4,09 (1H), 4,13 (1H), 4,98 (1H), 5,03 (1H), 5,13 (1H), 5,71 (1H), 6,44 (1H), 6,93 (1H) ppm.
1H-NMR (CDCl3) von B: δ = 0,00 (3H), 0,03 (3H), 0,88 (9H), 0,94 (3H), 1,03-1,72 (7H), 1,08 (3H), 1,17 (3H), 1,31 (3H), 1,39 (3H), 1,60+1,68 (3H), 1,89-2,08 (2H), 1,99 (3H), 2,17-2,51 (4H), 2,71 (3H), 2,74+2,87 (1H), 3,31 (1H), 3,57 (1H), 3,84 (1H), 3,95 (1H), 4,03-4,17 (2H), 4,98 (1H), 5,03 (1H), 5,13 (1H), 5,73 (1H), 6,46 (1H), 6,92 (1H) ppm.In analogy to example 1c, 2.07 g (8.61 mmol) of the compound shown in example 9b is mixed with 2.01 g (4.61 mmol) (2S, 6E / Z, 9S, 10E) -2.6, 10- Trimethyl-9 - [[dimethyl (1,1-dimethylethyl) silyl] oxy] -1-oxo-11- (2-methylthiazol-4-yl) -undeca-6,10-diene, which is analogous to has prepared the process described in DE 197 51 200.3 in order to isolate and after working up and purification, in addition to starting material, 995 mg (1.47 mmol, 32%) of the title compound A and 784 mg (1.16 mmol, 25%) of the title compound B in each case as a colorless oil.
1 H-NMR (CDCl 3 ) of A: δ = 0.01 (3H), 0.07 (3H), 0.85 (3H), 0.90 (9H), 0.98 (3H), 1, 00-2.33 (12H), 1.23 (3H), 1.33 (3H), 1.39 (3H), 1.60 + 1.67 (3H), 2.00 (3H), 2, 46 (1H), 2.72 (3H), 2.99 (1H), 3.34 (1H), 3.49 (1H), 3.87 (1H), 3.98 (1H), 4.09 (1H), 4.13 (1H), 4.98 (1H), 5.03 (1H), 5.13 (1H), 5.71 (1H), 6.44 (1H), 6.93 ( 1H) ppm.
1 H NMR (CDCl 3 ) of B: δ = 0.00 (3H), 0.03 (3H), 0.88 (9H), 0.94 (3H), 1.03-1.72 (7H ), 1.08 (3H), 1.17 (3H), 1.31 (3H), 1.39 (3H), 1.60 + 1.68 (3H), 1.89-2.08 (2H ), 1.99 (3H), 2.17-2.51 (4H), 2.71 (3H), 2.74 + 2.87 (1H), 3.31 (1H), 3.57 (1H ), 3.84 (1H), 3.95 (1H), 4.03-4.17 (2H), 4.98 (1H), 5.03 (1H), 5.13 (1H), 5, 73 (1H), 6.46 (1H), 6.92 (1H) ppm.

Beispiel 9dExample 9d (3S,6R,7S,8S,12E/Z,15S,16E)-15-[[Dimethyl(1,1-dimethylethyl)silyl]oxy]-1,3,7- trihydroxy-4,4,8,12,16-pentamethyl-17-(2-methylthiazol-4-yl)-6-(prop-2-en-1-yl)- heptadeca-12,16-dien-5-on(3S, 6R, 7S, 8S, 12E / Z, 15S, 16E) -15 - [[dimethyl (1,1-dimethylethyl) silyl] oxy] -1,3,7- trihydroxy-4,4,8,12,16-pentamethyl-17- (2-methylthiazol-4-yl) -6- (prop-2-en-1-yl) - heptadeca-12,16-dien-5-one

In Analogie zu Beispiel 1k setzt man 1,33 g (1,97 mmol) der nach Beispiel 9c dargestellten Verbindung A um und isoliert nach Aufarbeitung und Reinigung 1,02 g (1,60 mmol, 81%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = 0,01 (3H), 0,07 (3H), 0,89 (12H), 1,00-2,38 (12H), 1,04+1,07 (3H), 1,23+1,25 (3H), 1,60+1,68 (3H), 1,97+1,99 (3H), 2,52 (1H), 2,67-2,89 (1H), 2,73+2,77 (3H), 3,01 (1H), 3,33 (1H), 3,40-3,53 (1H), 3,74-3,93 (3H), 4,03-4,19 (2H), 5,00 (1H), 5,06 (1H), 5,10+5,20 (1H), 5,71 (1H), 6,42 (1H), 6,93 (1H) ppm.Analogously to Example 1k, 1.33 g (1.97 mmol) of the compound A prepared according to Example 9c is reacted and, after workup and purification, 1.02 g (1.60 mmol, 81%) of the title compound is isolated as a colorless oil.
1 H NMR (CDCl 3 ): δ = 0.01 (3H), 0.07 (3H), 0.89 (12H), 1.00-2.38 (12H), 1.04 + 1.07 (3H), 1.23 + 1.25 (3H), 1.60 + 1.68 (3H), 1.97 + 1.99 (3H), 2.52 (1H), 2.67-2, 89 (1H), 2.73 + 2.77 (3H), 3.01 (1H), 3.33 (1H), 3.40-3.53 (1H), 3.74-3.93 (3H ), 4.03-4.19 (2H), 5.00 (1H), 5.06 (1H), 5.10 + 5.20 (1H), 5.71 (1H), 6.42 (1H ), 6.93 (1H) ppm.

Beispiel 9eExample 9e (3S,6R,7S,8S,12E/Z,15S,16E)-1,3,7,15-Tetrakis-[[dimethyl(1,1- dimethylethyl)silyl]oxy]-4,4,8,12,16-pentamethyl-17-(2-methylthiazol-4-yl)-6- (prop-2-en-1-yl)-heptadeca-12,16-dien-5-on(3S, 6R, 7S, 8S, 12E / Z, 15S, 16E) -1,3,7,15-tetrakis - [[dimethyl (1,1- dimethylethyl) silyl] oxy] -4,4,8,12,16-pentamethyl-17- (2-methylthiazol-4-yl) -6- (prop-2-en-1-yl) -heptadeca-12,16-dien-5-one

In Analogie zu Beispiel 1l setzt man 1,02 g (1,60 mmol) der nach Beispiel 9d dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 1,46 g (1,49 mmol, 93%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = 0,00-0,11 (24H), 0,83-0,98 (39H), 1,01-1,62 (8H), 1,07 (3H), 1,20 (3H), 1,59+1,67 (3H), 1,97 (1H), 2,00 (3H), 2,19-2,34 (3H), 2,48 (1H), 2,72 (3H), 3,13 (1H), 3,57 (1H), 3,67 (1H), 3,78 (1H), 3,87 (1H), 4,09 (1H), 4,93 (1H), 4,99 (1H), 5,15 (1H), 5,77 (1H), 6,46 (1H), 6,91 (1H) ppm.Analogously to Example 1l, 1.02 g (1.60 mmol) of the compound shown in Example 9d is reacted and, after working up and purification, 1.46 g (1.49 mmol, 93%) of the title compound is isolated as a colorless oil.
1 H NMR (CDCl 3 ): δ = 0.00-0.11 (24H), 0.83-0.98 (39H), 1.01-1.62 (8H), 1.07 (3H) , 1.20 (3H), 1.59 + 1.67 (3H), 1.97 (1H), 2.00 (3H), 2.19-2.34 (3H), 2.48 (1H) , 2.72 (3H), 3.13 (1H), 3.57 (1H), 3.67 (1H), 3.78 (1H), 3.87 (1H), 4.09 (1H), 4.93 (1H), 4.99 (1H), 5.15 (1H), 5.77 (1H), 6.46 (1H), 6.91 (1H) ppm.

Beispiel 9fExample 9f (3S,6R,7S,8S,12E/Z,15S,16E)-1-Hydroxy-3,7,15-tris-[[dimethyl(1,1- dimethylethyl)silyl]oxy]-4,4,8,12,16-pentamethyl-17-(2-methylthiazol-4-yl)-6- (prop-2-en-1-yl)-heptadeca-12,16-dien-5-on(3S, 6R, 7S, 8S, 12E / Z, 15S, 16E) -1-hydroxy-3,7,15-tris - [[dimethyl (1,1- dimethylethyl) silyl] oxy] -4,4,8,12,16-pentamethyl-17- (2-methylthiazol-4-yl) -6- (prop-2-en-1-yl) -heptadeca-12,16-dien-5-one

In Analogie zu Beispiel 1m setzt man 1,45 g (1,48 mmol) der nach Beispiel 9e dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 1,19 g (1,37 mmol, 93%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = -0,01-0,14 (18H), 0,82-0,97 (30H), 1,04-1,70 (7H), 1,09 (3H), 1,19 (3H), 1,59+1,68 (3H), 1,84-2,08 (3H), 2,00 (3H), 2,18-2,36 (3H), 2,47 (1H), 2,71 (3H), 3,13 (1H), 3,66 (2H), 3,80 (1H), 4,04 (1H), 4,10 (1H), 4,96 (1H), 5,01 (1H), 5,14 (1H), 5,77 (1H), 6,46 (1H), 6,92 (1H) ppm.Analogously to Example 1m, 1.45 g (1.48 mmol) of the compound shown in Example 9e is reacted and, after workup and purification, 1.19 g (1.37 mmol, 93%) of the title compound is isolated as a colorless oil.
1 H NMR (CDCl 3 ): δ = -0.01-0.14 (18H), 0.82-0.97 (30H), 1.04-1.70 (7H), 1.09 (3H ), 1.19 (3H), 1.59 + 1.68 (3H), 1.84-2.08 (3H), 2.00 (3H), 2.18-2.36 (3H), 2 , 47 (1H), 2.71 (3H), 3.13 (1H), 3.66 (2H), 3.80 (1H), 4.04 (1H), 4.10 (1H), 4, 96 (1H), 5.01 (1H), 5.14 (1H), 5.77 (1H), 6.46 (1H), 6.92 (1H) ppm.

Beispiel 9gExample 9g (3S,6R,7S,8S,12E/Z,15S,16E)-3,7,15-Tris-[[dimethyl(1,1-dimethylethyl)silyl]oxy]- 4,4,8,12,16-pentamethyl-17-(2-methylthiazol-4-yl)-5-oxo-6-(prop-2-en-1-yl)- heptadeca-12,16-dienal(3S, 6R, 7S, 8S, 12E / Z, 15S, 16E) -3,7,15-tris - [[dimethyl (1,1-dimethylethyl) silyl] oxy] - 4,4,8,12,16-pentamethyl-17- (2-methylthiazol-4-yl) -5-oxo-6- (prop-2-en-1-yl) - heptadeca-12,16-dienal

In Analogie zu Beispiel 1n setzt man 1,18 g (1,37 mmol) der nach Beispiel 9f dargestellten Verbindung um und isoliert nach Aufarbeitung 1,25 g (max. 1,37 mmol) der Titelverbindung als gelbes Öl, das man ohne Reinigung weiter umsetzt.Analogously to Example 1n, 1.18 g (1.37 mmol) of that according to Example 9f is used compound shown and isolated after working up 1.25 g (max. 1.37 mmol) the title compound as a yellow oil that you can continue without purification implements.

Beispiel 9hExample 9h (3S,6R,7S,8S,12Z,15S,16E)-3,7,15-Tris-[[dimethyl(1,1-dimethylethyl)silyl]oxy]- 4,4,8,12,16-pentamethyl-17-(2-methylthiazol-4-yl)-5-oxo-6-(prop-2-en-1-yl)- heptadeca-12,16-diensäure (A) und (3S,6R,7S,8S,12E,15S,16E)-3,7,15-Tris- ([dimethyl(1,1-dimethylethyl)silyl]oxy]-4,4,8,12,16-pentamethyl-17-(2- methylthiazol-4-yl)-5-oxo-6-(prop-2-en-1-yl)-heptadeca-12,16-diensäure (B)(3S, 6R, 7S, 8S, 12Z, 15S, 16E) -3,7,15-tris - [[dimethyl (1,1-dimethylethyl) silyl] oxy] - 4,4,8,12,16-pentamethyl-17- (2-methylthiazol-4-yl) -5-oxo-6- (prop-2-en-1-yl) - heptadeca-12,16-dienoic acid (A) and (3S, 6R, 7S, 8S, 12E, 15S, 16E) -3,7,15-tris- ([dimethyl (1,1-dimethylethyl) silyl] oxy] -4,4,8,12,16-pentamethyl-17- (2- methylthiazol-4-yl) -5-oxo-6- (prop-2-en-1-yl) -heptadeca-12,16-dienoic acid (B)

In Analogie zu Beispiel 10 setzt man 1,25 g (max. 1,37 mmol) der nach Beispiel 9g dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 302 mg (0,34 mmol, 25%) der Titelverbindung A sowie 230 mg (0,26 mmol, 19%) der Titelverbindung B jeweils als farbloses Öl.
1H-NMR (CDCl3) von A: δ = -0,02-0,15 (18H), 0,82-0,97 (30H), 1,05-2,53 (14H), 1,12 (3H), 1,17 (3H), 1,70 (3H), 1,96 (3H), 2,71 (3H), 3,17 (1H), 3,72 (1H), 4,16 (1H), 4,37 (1H), 4,94 (1H), 4,99 (1H), 5,20 (1H), 5,73 (1H), 6,66 (1H), 6,93 (1H) ppm.
1H-NMR (CDCl3) von B: δ = -0,03-0,15 (18H), 0,81-0,95 (30H), 1,01-2,50 (13H), 1,12 (3H), 1,18 (3H), 1,57 (3H), 1,95 (3H), 2,60 (1H), 2,70 (3H), 3,22 (1H), 3,79 (1H), 4,08 (1H), 4,32 (1H), 4,94 (1H), 5,00 (1H), 5,11 (1H), 5,74 (1H), 6,46 (1H), 6,93 (1H) ppm.Analogously to Example 10, 1.25 g (max. 1.37 mmol) of the compound shown in Example 9g is reacted and, after workup and purification, 302 mg (0.34 mmol, 25%) of the title compound A and 230 mg ( 0.26 mmol, 19%) of the title compound B in each case as a colorless oil.
1 H NMR (CDCl 3 ) of A: δ = -0.02-0.15 (18H), 0.82-0.97 (30H), 1.05-2.53 (14H), 1.12 (3H), 1.17 (3H), 1.70 (3H), 1.96 (3H), 2.71 (3H), 3.17 (1H), 3.72 (1H), 4.16 ( 1H), 4.37 (1H), 4.94 (1H), 4.99 (1H), 5.20 (1H), 5.73 (1H), 6.66 (1H), 6.93 (1H) ) ppm.
1 H NMR (CDCl 3 ) of B: δ = -0.03-0.15 (18H), 0.81-0.95 (30H), 1.01-2.50 (13H), 1.12 (3H), 1.18 (3H), 1.57 (3H), 1.95 (3H), 2.60 (1H), 2.70 (3H), 3.22 (1H), 3.79 ( 1H), 4.08 (1H), 4.32 (1H), 4.94 (1H), 5.00 (1H), 5.11 (1H), 5.74 (1H), 6.46 (1H) ), 6.93 (1H) ppm.

Beispiel 9iExample 9i (3S,6R,7S,8S,12Z,15S,16E)-3,7-Bis-[[dimethyl(1,1-dimethylethyl)silyl]oxy]-15- hydroxy-4,4,8,12,16-pentamethyl-17-(2-methylthiazol-4-yl)-5-oxo-6-(prop-2-en- 1-yl)-heptadeca-12,16-diensäure(3S, 6R, 7S, 8S, 12Z, 15S, 16E) -3,7-bis - [[dimethyl (1,1-dimethylethyl) silyl] oxy] -15- hydroxy-4,4,8,12,16-pentamethyl-17- (2-methylthiazol-4-yl) -5-oxo-6- (prop-2-en- 1-yl) -heptadeca-12,16-dienoic acid

In Analogie zu Beispiel 1e setzt man 302 mg (0,34 mmol) der nach Beispiel 9h dargestellten Verbindung A um und isoliert nach Aufarbeitung 296 mg (max. 0,34 mmol) der Titelverbindung als blass gelbes Öl, das man ohne Reinigung weiter umsetzt.Analogously to Example 1e, 302 mg (0.34 mmol) of that from Example 9h are used Compound A shown and isolated after working up 296 mg (max.  0.34 mmol) of the title compound as a pale yellow oil, which one without purification continues to implement.

Beispiel 9jExample 9j (4S,7R,8S,9S,13Z,16S(E))-4,8-Bis-[[dimethyl(1,1-dimethylethyl)silyl]oxy]-16-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en- 1-yl)-cyclohexadec-13-en-2,6-dion(4S, 7R, 8S, 9S, 13Z, 16S (E)) - 4,8-bis - [[dimethyl (1,1-dimethylethyl) silyl] oxy] -16- (1- methyl-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa-5,5,9,13-tetramethyl-7- (prop-2-en- 1-yl) -cyclohexadec-13-en-2,6-dione

In Analogie zu Beispiel 1q setzt man 296 mg (max. 0,34 mmol) der nach Beispiel 9i dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 166 mg (0,22 mmol, 65%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = -0,10 (3H), 0,09 (3H), 0,11 (3H), 0,13 (3H), 0,86 (9H), 0,80-2,85 (13H), 0,94 (9H), 1,00 (3H), 1,10 (3H), 1,20 (3H), 1,68 (3H), 2,10 (3H), 2,71 (3H), 3,11 (1H), 4,01 (2H), 4,85-5,03 (3H) 5,16 (1H), 5,78 (1H), 6,57 (1H), 6,98 (1H) ppm.Analogously to Example 1q, 296 mg (max. 0.34 mmol) of the compound shown in Example 9i are reacted and, after workup and purification, 166 mg (0.22 mmol, 65%) of the title compound are isolated as a colorless oil.
1 H NMR (CDCl 3 ): δ = -0.10 (3H), 0.09 (3H), 0.11 (3H), 0.13 (3H), 0.86 (9H), 0.80 -2.85 (13H), 0.94 (9H), 1.00 (3H), 1.10 (3H), 1.20 (3H), 1.68 (3H), 2.10 (3H), 2.71 (3H), 3.11 (1H), 4.01 (2H), 4.85-5.03 (3H) 5.16 (1H), 5.78 (1H), 6.57 (1H ), 6.98 (1H) ppm.

Beispiel 9Example 9 (4S,7R,8S,9S,13Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en- 2,6-dion(4S, 7R, 8S, 9S, 13Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methylthiazole-4- yl) ethenyl) -1-oxa-5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) -cyclohexadec-13-en- 2,6-dione

In Analogie zu Beispiel 1 setzt man 25 mg (34 µmol) der nach Beispiel 9j dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 10 mg (19 µmol, 57%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = 1,03 (3H), 1,05 (3H), 1,20-2,74 (14H), 1,30 (3H), 1,69 (3H), 2,07 (3H), 2,69 (3H), 3,33 (1H), 3,69 (1H), 3,72 (1H), 4,23 (1H), 5,02 (1H), 5,07 (1H), 5,12 (1H), 5,21 (1H), 5,76 (1H), 6,57 (1H), 6,96 (1H) ppm.Analogously to Example 1, 25 mg (34 μmol) of the compound shown in Example 9j is reacted and, after workup and purification, 10 mg (19 μmol, 57%) of the title compound is isolated as a colorless oil.
1 H-NMR (CDCl 3 ): δ = 1.03 (3H), 1.05 (3H), 1.20-2.74 (14H), 1.30 (3H), 1.69 (3H), 2.07 (3H), 2.69 (3H), 3.33 (1H), 3.69 (1H), 3.72 (1H), 4.23 (1H), 5.02 (1H), 5 , 07 (1H), 5.12 (1H), 5.21 (1H), 5.76 (1H), 6.57 (1H), 6.96 (1H) ppm.

Beispiel 10Example 10 (1S,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion (A) und (1R,3S(E),7S,10R,11S,12S,16S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion (B)(1S, 3S (E), 7S, 10R, 11S, 12S, 16R) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- methyl-2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17- dioxabicyclo [14.1.0] heptadecane-5,9-dione (A) and (1R, 3S (E), 7S, 10R, 11S, 12S, 16S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- methyl-2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17- dioxabicyclo [14.1.0] heptadecane-5,9-dione (B)

Die Lösung von 8,0 mg (15,5 µmol) der nach Beispiel 9 dargestellten Verbindung in 1 ml Acetonitril versetzt man mit 89 µl einer 1 M Lösung von Natriumethylendiamin-tetracetat, kühlt auf 0°C und versetzt mit 148 µl 1,1,1- Trifluoraceton sowie einem Gemisch aus 22 mg Oxon und 41 mg Natriumhydrogencarbonat. Man läßt 5 Stunden reagieren, gießt auf Natriumthiosulfatlösung und extrahiert mehrfach mit Ethylacetat. Die vereinigten organischen Extrakte wäscht man mit gesättigter Natriumchloridlösung und reinigt den nach Filtration und Lösungsmittelabzug erhaltenen Rückstand durch Chromatographie an einer analytischen Dünnschichtplatte. Als Laufmittel dient ein Gemisch aus n-Hexan und Ethylacetat. Isoliert werden 3,2 mg (6 µmol, 39%) der Titelverbindung A sowie 1,0 mg (2 µmol, 12%) der Titelverbindung B jeweils als farbloses Öl.
1H-NMR (CDCl3) von A: δ = 1,00 (3H), 1,02 (3H), 1,21-1,82 (7H), 1,29 (3H), 1,36 (3H), 1,95-2,06 (2H), 2,11 (3H), 2,30 (1H), 2,40 (1H), 2,48-2,62 (2H), 2,72 (3H), 2,81 (2H), 3,50 (1H), 3,69 (1H), 4,27 (1H), 4,52 (1H), 5,01 (1H), 5,06 (1H), 5,46 (1H), 5,72 (1H), 6,59 (1H), 6,99 (1H) ppm.
1H-NMR (CDCl3) von B: δ = 0,96 (3H), 1,00 (3H), 1,20-1,91 (8H), 1,29 (3H), 1,34 (3H), 2,04 (1H), 2,09 (3H), 2,33 (1H), 2,42-2,61 (3H), 2,76 (3H), 2,93 (1H), 2,96 (1H), 3,38 (1H), 3,68 (1H), 3,99 (1H), 4,29 (1H), 4,98 (1H), 5,01 (1H), 5,57 (1H), 5,74 (1H), 6,69 (1H), 7,01 (1H) ppm.The solution of 8.0 mg (15.5 μmol) of the compound shown in Example 9 in 1 ml of acetonitrile is mixed with 89 μl of a 1 M solution of sodium ethylenediamine tetracetate, cooled to 0 ° C. and treated with 148 μl of 1.1 , 1-trifluoroacetone and a mixture of 22 mg oxone and 41 mg sodium hydrogen carbonate. The mixture is left to react for 5 hours, poured onto sodium thiosulfate solution and extracted several times with ethyl acetate. The combined organic extracts are washed with saturated sodium chloride solution and the residue obtained after filtration and removal of the solvent is purified by chromatography on an analytical thin-layer plate. A mixture of n-hexane and ethyl acetate is used as the eluent. 3.2 mg (6 μmol, 39%) of the title compound A and 1.0 mg (2 μmol, 12%) of the title compound B are each isolated as a colorless oil.
1 H NMR (CDCl 3 ) of A: δ = 1.00 (3H), 1.02 (3H), 1.21-1.82 (7H), 1.29 (3H), 1.36 (3H ), 1.95-2.06 (2H), 2.11 (3H), 2.30 (1H), 2.40 (1H), 2.48-2.62 (2H), 2.72 (3H ), 2.81 (2H), 3.50 (1H), 3.69 (1H), 4.27 (1H), 4.52 (1H), 5.01 (1H), 5.06 (1H) , 5.46 (1H), 5.72 (1H), 6.59 (1H), 6.99 (1H) ppm.
1 H NMR (CDCl 3 ) of B: δ = 0.96 (3H), 1.00 (3H), 1.20-1.91 (8H), 1.29 (3H), 1.34 (3H) ), 2.04 (1H), 2.09 (3H), 2.33 (1H), 2.42-2.61 (3H), 2.76 (3H), 2.93 (1H), 2, 96 (1H), 3.38 (1H), 3.68 (1H), 3.99 (1H), 4.29 (1H), 4.98 (1H), 5.01 (1H), 5.57 (1H), 5.74 (1H), 6.69 (1H), 7.01 (1H) ppm.

Beispiel 11Example 11 (4S,7R,8S,9S,13E,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en- 2,6-dion(4S, 7R, 8S, 9S, 13E, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methylthiazole-4- yl) ethenyl) -1-oxa-5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) -cyclohexadec-13-en- 2,6-dione Beispiel 11aExample 11a (3S,6R,7S,8S,12E,15S,16E)-3,7-Bis-[[dimethyl(1,1-dimethylethyl)silyl]oxy]-15- hydroxy-4,4,8,12,16-pentamethyl-17-(2-methylthiazol-4-yl)-5-oxo-6-(prop-2-en- 1-yl)-heptadeca-12,16-diensäure(3S, 6R, 7S, 8S, 12E, 15S, 16E) -3,7-bis - [[dimethyl (1,1-dimethylethyl) silyl] oxy] -15- hydroxy-4,4,8,12,16-pentamethyl-17- (2-methylthiazol-4-yl) -5-oxo-6- (prop-2-en- 1-yl) -heptadeca-12,16-dienoic acid

In Analogie zu Beispiel 1e setzt man 230 mg (0,26 mmol) der nach Beispiel 9h dargestellten Verbindung B um und isoliert nach Aufarbeitung 214 mg (max. 0,26 mmol) der Titelverbindung als blass gelbes Öl, das man ohne Reinigung weiter umsetzt.In analogy to Example 1e, 230 mg (0.26 mmol) of that according to Example 9h are used Compound B shown and isolated after processing 214 mg (max.  0.26 mmol) of the title compound as a pale yellow oil, which one without purification continues to implement.

Beispiel 11bExample 11b (4S,7R,8S,9S,13E,16S(E))-4,8-Bis-[[dimethyl(1,1-dimethylethyl)silyl]oxy]-16-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en- 1-yl)-cyclohexadec-13-en-2,6-dion(4S, 7R, 8S, 9S, 13E, 16S (E)) - 4,8-bis - [[dimethyl (1,1-dimethylethyl) silyl] oxy] -16- (1- methyl-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa-5,5,9,13-tetramethyl-7- (prop-2-en- 1-yl) -cyclohexadec-13-en-2,6-dione

In Analogie zu Beispiel 1q setzt man 214 mg (max. 0,26 mmol) der nach Beispiel 11a dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 114 mg (0,15 mmol, 59%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = 0,05 (3H), 0,08 (3H), 0,10 (3H), 0,13 (3H), 0,82-0,94 (21H), 1,12 (3H), 1,15-2,62 (13H), 1,21 (3H), 1,59 (3H), 2,11 (3H), 2,71 (3H), 3,03 (1H), 3,87 (1H), 4,30 (1H), 4,99 (1H), 5,03 (1H), 5,21 (1H), 5,28 (1H), 5,79 (1H), 6,51 (1H), 6,91 (1H) ppm.Analogously to Example 1q, 214 mg (max. 0.26 mmol) of the compound shown in Example 11a are reacted and, after working up and purification, 114 mg (0.15 mmol, 59%) of the title compound is isolated as a colorless oil.
1 H-NMR (CDCl 3 ): δ = 0.05 (3H), 0.08 (3H), 0.10 (3H), 0.13 (3H), 0.82-0.94 (21H), 1.12 (3H), 1.15-2.62 (13H), 1.21 (3H), 1.59 (3H), 2.11 (3H), 2.71 (3H), 3.03 ( 1H), 3.87 (1H), 4.30 (1H), 4.99 (1H), 5.03 (1H), 5.21 (1H), 5.28 (1H), 5.79 (1H) ), 6.51 (1H), 6.91 (1H) ppm.

Beispiel 11Example 11 (4S,7R,8S,9S,13E,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en- 2,6-dion(4S, 7R, 8S, 9S, 13E, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methylthiazole-4- yl) ethenyl) -1-oxa-5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) -cyclohexadec-13-en- 2,6-dione

In Analogie zu Beispiel 1 setzt man 15 mg (20 µmol) der nach Beispiel 11b dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 7,3 mg (14 µmol, 71%) der Titelverbindung als farbloses Öl.
1H-NMR (CDCl3): δ = 0,80-2,62 (13H), 0,99 (3H), 1,01 (3H), 1,26 (3H), 1,60 (3H), 2,04 (3H), 2,69 (3H), 3,49 (1H), 3,73 (1H), 4,01 (1H), 4,12 (1H), 4,42 (1H), 4,94-5,10 (3H), 5,37 (1H), 5,71 (1H), 6,56 (1H), 6,99 (1H) ppm.Analogously to Example 1, 15 mg (20 μmol) of the compound shown in Example 11b is reacted and, after workup and purification, 7.3 mg (14 μmol, 71%) of the title compound is isolated as a colorless oil.
1 H-NMR (CDCl 3 ): δ = 0.80-2.62 (13H), 0.99 (3H), 1.01 (3H), 1.26 (3H), 1.60 (3H), 2.04 (3H), 2.69 (3H), 3.49 (1H), 3.73 (1H), 4.01 (1H), 4.12 (1H), 4.42 (1H), 4 , 94-5.10 (3H), 5.37 (1H), 5.71 (1H), 6.56 (1H), 6.99 (1H) ppm.

Beispiel 12Example 12 (1R,3S(E),7S,10R,11S,12S,16R)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,15-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion (A) und (1S,3S(E),7S,10R,11S,12S,16S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion (B)(1R, 3S (E), 7S, 10R, 11S, 12S, 16R) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- methyl-2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,15-tetramethyl-4,17- dioxabicyclo [14.1.0] heptadecane-5,9-dione (A) and (1S, 3S (E), 7S, 10R, 11S, 12S, 16S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- methyl-2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17- dioxabicyclo [14.1.0] heptadecane-5,9-dione (B)

In Analogie zu Beispiel 10 setzt man 7,3 mg (14 µmol) der nach Beispiel 11 dargestellten Verbindung um und isoliert nach Aufarbeitung und Reinigung 2,3 mg (4,3 µmol, 31%) der Titelverbindung A (oder B) sowie 2,0 mg (3,7 µmol, 27%) der Titelverbindung B (oder A) jeweils als farbloses Öl.
1H-NMR (CDCl3) von A (oder B): δ = 0,90-2,34 (10H), 0,95 (3H), 1,01 (3H), 1,29 (3H), 1,38 (3H), 2,10 (3H), 2,47-2,62 (3H), 2,72 (3H), 2,88 (2H), 3,48 (1H), 3,80 (1H), 4,19 (1H), 4,32 (1H), 5,02 (1H), 5,07 (1H), 5,48 (1H), 5,77 (1H), 6,63 (1H), 7,00 (1H) ppm.
1H-NMR (CDCl3) von B (oder A): δ = 0,97 (3H), 1,06 (3H), 1,20-2,12 (9H), 1,25 (3H), 1,34 (3H), 2,08 (3H), 2,28 (1H), 2,46-2,62 (3H), 2,72 (3H), 2,92 (2H), 3,40 (1H), 3,68 (1H), 3,75 (1H), 4,28 (1H), 5,01 (1H), 5,06 (1H), 5,44 (1H), 5,72 (1H), 6,62 (1H), 6,99 (1H) ppm.Analogously to Example 10, 7.3 mg (14 μmol) of the compound shown in Example 11 are reacted and, after workup and purification, 2.3 mg (4.3 μmol, 31%) of the title compound A (or B) and 2 , 0 mg (3.7 µmol, 27%) of the title compound B (or A) in each case as a colorless oil.
1 H NMR (CDCl 3 ) of A (or B): δ = 0.90-2.34 (10H), 0.95 (3H), 1.01 (3H), 1.29 (3H), 1 , 38 (3H), 2.10 (3H), 2.47-2.62 (3H), 2.72 (3H), 2.88 (2H), 3.48 (1H), 3.80 (1H ), 4.19 (1H), 4.32 (1H), 5.02 (1H), 5.07 (1H), 5.48 (1H), 5.77 (1H), 6.63 (1H) , 7.00 (1H) ppm.
1 H NMR (CDCl 3 ) of B (or A): δ = 0.97 (3H), 1.06 (3H), 1.20-2.12 (9H), 1.25 (3H), 1 , 34 (3H), 2.08 (3H), 2.28 (1H), 2.46-2.62 (3H), 2.72 (3H), 2.92 (2H), 3.40 (1H ), 3.68 (1H), 3.75 (1H), 4.28 (1H), 5.01 (1H), 5.06 (1H), 5.44 (1H), 5.72 (1H) , 6.62 (1H), 6.99 (1H) ppm.

Claims (8)

1. Epothilon-Derivate der allgemeinen Formel I,
worin
R1a, R1b gleich oder verschieden sind und Wasserstoff, C1-C10-Alkyl, Aryl, C7-C20-Aralkyl, oder gemeinsam eine -(CH2)m-Gruppe mit m = 1, 2, 3, 4 oder 5, eine -(CH2)-O-(CH2)-Gruppe,
R2a Wasserstoff, C1-C10-Alkyl, Aryl, C7-C20-Aralkyl, -(CH2)ra-C ∼ C-(CH2)pa- R26a, -(CH2)ra-C=C-(CH2)pa-R26a
R2b -(CH2)rb-C∼C-(CH2)pb-R26b, -(CH2)rb-C=C-(CH2)pb-R26b,
ra, rb gleich oder verschieden sind und 0 bis 4,
pa, pb gleich oder verschieden sind und 0 bis 3,
n 0 bis 5,
R3a Wasserstoff, C1-C10-Alkyl, Aryl, C7-C20-Aralkyl,
R14 Wasserstoff, OR14a, Hal,
R3b OPG14,
R4 Wasserstoff, C1-C10-Alkyl, Aryl, C7-C20-Aralkyl, Hal, OR25, CN,
R25 Wasserstoff, eine Schutzgruppe PG5,
R26a, R26b gleich oder verschieden sind und Wasserstoff, C1-C10-Alkyl, Aryl, C7-C20-Aralkyl, C1-C10-Acyl, oder, falls pa bzw. pb <0 sind, eine Gruppe OR27,
R27 Wasserstoff, eine Schutzgruppe PG6,
R5 Wasserstoff, C1-C10-Alkyl, Aryl, C2-C20-Aralkyl, (CH2)s-A,
wobei s für 1, 2, 3 oder 4,
A für OR22 oder Hal,
R22 für Wasserstoff oder PG4 stehen,
R6, R7 je ein Wasserstoffatom, gemeinsam eine zusätzliche Bindung oder ein Sauerstoffatom,
R8 Wasserstoff, Halogen, CN, C1-C20-Alkyl, Aryl, C7-C20-Aralkyl, die alle substituiert sein können,
X ein Sauerstoffatom, zwei Alkoxygruppen OR23, eine C2-C10-Alkylen-α,ω- dioxygruppe, die geradkettig oder verzweigt sein kann, H/OR9 oder eine Gruppierung CR10R11,
wobei
R23 für einen C1-C20-Alkylrest,
R9 für Wasserstoff oder eine Schutzgruppe PGx,
R10, R11 gleich oder verschieden sind und für Wasserstoff, einen C1-C20- Alkyl-, Aryl-, C7-C20-Aralkylrest oder R10 und R11 zusammen mit dem Methylenkohlenstoffatom gemeinsam für einen 5- bis 7- gliedrigen carbocyclischen Ring stehen,
Y ein Sauerstoffatom oder zwei Wasserstoffatome,
Z ein Sauerstoffatom oder H/OR12,
wobei
R12 Wasserstoff oder eine Schutzgruppe PGz ist,
Hal Halogen, vorzugsweise Fluor, Chlor, Brom oder Iod, bedeuten.1. epothilone derivatives of the general formula I,
wherein
R 1a , R 1b are identical or different and are hydrogen, C 1 -C 10 alkyl, aryl, C 7 -C 20 aralkyl, or together a - (CH 2 ) m group with m = 1, 2, 3, 4 or 5, a - (CH 2 ) -O- (CH 2 ) group,
R 2a is hydrogen, C 1 -C 10 alkyl, aryl, C 7 -C 20 aralkyl, - (CH 2 ) ra -C ∼ C- (CH 2 ) pa - R 26a , - (CH 2 ) ra -C = C- (CH 2 ) pa -R 26a
R 2b - (CH 2 ) rb -C∼C- (CH 2 ) pb -R 26b , - (CH 2 ) rb -C = C- (CH 2 ) pb -R 26b ,
ra, rb are the same or different and 0 to 4,
pa, pb are the same or different and 0 to 3,
n 0 to 5,
R 3a is hydrogen, C 1 -C 10 alkyl, aryl, C 7 -C 20 aralkyl,
R 14 is hydrogen, OR 14a , Hal,
R 3b OPG 14 ,
R 4 is hydrogen, C 1 -C 10 alkyl, aryl, C 7 -C 20 aralkyl, Hal, OR 25 , CN,
R 25 is hydrogen, a protective group PG 5 ,
R 26a , R 26b are the same or different and are hydrogen, C 1 -C 10 alkyl, aryl, C 7 -C 20 aralkyl, C 1 -C 10 acyl, or, if pa or pb <0, one Group OR 27 ,
R 27 is hydrogen, a protective group PG 6 ,
R 5 is hydrogen, C 1 -C 10 alkyl, aryl, C 2 -C 20 aralkyl, (CH 2 ) s -A,
where s is 1, 2, 3 or 4,
A for OR 22 or Hal,
R 22 represents hydrogen or PG 4 ,
R 6 , R 7 each represent a hydrogen atom, together an additional bond or an oxygen atom,
R 8 is hydrogen, halogen, CN, C 1 -C 20 alkyl, aryl, C 7 -C 20 aralkyl, all of which can be substituted,
X is an oxygen atom, two alkoxy groups OR 23 , a C 2 -C 10 alkylene-α, ω- dioxy group, which can be straight-chain or branched, H / OR 9 or a group CR 10 R 11 ,
in which
R 23 represents a C 1 -C 20 alkyl radical,
R 9 represents hydrogen or a protective group PG x ,
R 10 , R 11 are the same or different and are hydrogen, a C 1 -C 20 alkyl, aryl, C 7 -C 20 aralkyl radical or R 10 and R 11 together with the methylene carbon atom together for a 5 to 7 - membered carbocyclic ring,
Y is an oxygen atom or two hydrogen atoms,
Z is an oxygen atom or H / OR 12 ,
in which
R 12 is hydrogen or a protective group PG z ,
Hal is halogen, preferably fluorine, chlorine, bromine or iodine. 2. Verbindungen der allgemeinen Formel I nach Anspruch 1, dadurch gekennzeichnet, daß R2a für ein Wasserstoffatom steht.2. Compounds of general formula I according to claim 1, characterized in that R 2a represents a hydrogen atom. 3. Verbindungen der allgemeinen Formel I nach Anspruch 1, dadurch gekennzeichnet, daß R1a und R1b jeweils für eine Methylgruppe stehen oder gemeinsam eine Trimethylengruppe bilden.3. Compounds of general formula I according to claim 1, characterized in that R 1a and R 1b each represent a methyl group or together form a trimethylene group. 4. Verbindungen der allgemeinen Formel I nach Anspruch 1, dadurch gekennzeichnet, daß R8 ein Halogenatom oder eine Nitrilgruppe ist.4. Compounds of general formula I according to claim 1, characterized in that R 8 is a halogen atom or a nitrile group. 5. Verbindungen nach Anspruch 4, dadurch gekennzeichnet, daß R8 ein Fluoratom ist.5. Compounds according to claim 4, characterized in that R 8 is a fluorine atom. 6. Verbindungen der allgemeinen Formel I nach Anspruch 1, nämlich
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- fluor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)- 1-oxa-5,5-trimethylen-9,13-dimethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-pyridyl)ethenyl)-1-oxa- 5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(2-(2- pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9- dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-13-ethyl-16-(1-methyl-2-(2- pyridyl)ethenyl)-1-oxa-5,5,9-trimethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-16-ethyl-10-(but-3-in-1-yl)- 3-(1-methyl-2-(2-pyridyl)ethenyl)-8,8,12-trimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-pyridyl)ethenyl)-1-oxa- 5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(2-(2- pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9- dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- fluor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- chlor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-pyridyl)ethenyl)-1-oxa- 5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(2-(2- pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9- dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- fluor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- chlor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2- pyridyl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-pyridyl)ethenyl)-1-oxa- 5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2- pyridyl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-fluor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2- pyridyl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-chlor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-pyridyl)ethenyl)-1-oxa- 5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(2- (2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan- 5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- fluor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- chlor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-pyridyl)ethenyl)-1-oxa- 5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(2- (2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan- 5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- fluor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-pyridyl)ethenyl)-1- oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- chlor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2- pyridyl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-methyl-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl- 4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-pyridyl)ethenyl)-1-oxa- 5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2- pyridyl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-fluor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl- 4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2- pyridyl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-chlor-2-(2-pyridyl)ethenyl)-8,8,12,16-tetramethyl- 4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methylthiazol-4-yl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(2-(2- methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- chlor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methylthiazol-4-yl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(2-(2- methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- chlor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion (4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-
methylthiazol-4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1- ethyl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol- 4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methylthiazol- 4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-chlor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methylthiazol-4-yl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(2- (2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- chlor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methylthiazol-4-yl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(2- (2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- chlor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2- methylthiazol-4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16- tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)-cyclohexadec- 13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16- tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol- 4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16- tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methylthiazol- 4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-chlor-2-(2-methylthiazol-4-yl)ethenyl)-8,8,12,16- tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- methyl-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methyloxazol-4-yl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(2-(2- methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- fluor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- chlor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- methyl-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methyloxazol-4-yl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(2-(2- methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- fluor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(but-3-en-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-en-1-yl)-3-(1- chlor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2- methyloxazol-4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1- ethyl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-methyl-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methyloxazol- 4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-fluor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methyloxazol- 4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(2-oxacyclopropyl-1-ethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10-(2-oxacyclopropyl- 1-ethyl)-3-(1-chlor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- methyl-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methyloxazol-4-yl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(2- (2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- fluor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- chlor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- methyl-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methyloxazol-4-yl)ethenyl)- 1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(2- (2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- fluor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en- 2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- chlor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16-tetramethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2- methyloxazol-4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-methyl-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16- tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)-cyclohexadec- 13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16- tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methyloxazol- 4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-fluor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16- tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methyloxazol- 4-yl)ethenyl)-1-oxa-5,5,9,13-tetramethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-chlor-2-(2-methyloxazol-4-yl)ethenyl)-8,8,12,16- tetramethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-pyridyl)ethenyl)- 1-oxa-5,5-trimethylen-9,13-dimethyl-7-(but-3-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(but-3-in-1-yl)-3-(1- methyl-2-(2-pyridyl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-pyridyl)ethenyl)-1- oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- fluor-2-(2-pyridyl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-pyridyl)ethenyl)-1- oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- fluor-2-(2-pyridyl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2- pyridyl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-fluor-2-(2-pyridyl)ethenyl)-8,8-trimethylen-12,16- dimethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-in-1-yl)-cyclohexadec- 13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- methyl-2-(2-methylthiazol-4-yl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol-4- yl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-in-1-yl)-cyclohexadec- 13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methylthiazol-4-yl)ethenyl)- 1-oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-en-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(2- (2-methylthiazol-4-yl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methylthiazol- 4-yl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-fluor-2-(2-methylthiazol-4-yl)ethenyl)-8,8- trimethylen-12,16-dimethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methyloxazol-4-yl)ethenyl)- 1-oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-in-1-yl)-cyclohexadec-13-en-2,6- dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(2- (2-methyloxazol-4-yl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-in-1-yl)-cyclohexadec- 13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-in-1-yl)-3-(1- fluor-2-(2-methyloxazol-4-yl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-methyl-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-en-1-yl)-cyclohexadec- 13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- methyl-2-(2-methyloxazol-4-yl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R,8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-fluor-2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(prop-2-en-1-yl)-cyclohexadec- 13-en-2,6-dion
(1S/R,3S(E),7S,10R,11R,12S,16R/S)-7,11-Dihydroxy-10-(prop-2-en-1-yl)-3-(1- fluor-2-(2-methyloxazol-4-yl)ethenyl)-8,8-trimethylen-12,16-dimethyl-4,17- dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(2-(2-methyloxazol-4- yl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(2-(2-methyloxazol-4-yl)ethenyl)-8,8-trimethylen- 12,16-dimethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion
(4S,7R(RS),8S,9S,13E/Z,16S(E))-4,8-Dihydroxy-16-(1-chlor-2-(2-methyloxazol- 4-yl)ethenyl)-1-oxa-5,5-trimethylen-9,13-dimethyl-7-(oxacyclopropylmethyl)- cyclohexadec-13-en-2,6-dion
(1S/R,3S(E),7S,10R(RS),11R,12S,16R/S)-7,11-Dihydroxy-10- (oxacyclopropylmethyl)-3-(1-chlor-2-(2-methyloxazol-4-yl)ethenyl)-8,8- trimethylen-12,16-dimethyl-4,17-dioxabicyclo[14.1.0]heptadecan-5,9-dion.6. Compounds of general formula I according to claim 1, namely
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-methyl- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-methyl- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1-methyl- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-fluoro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-fluoro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) - 1-oxa-5,5- trimethylene-9,13-dimethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-methyl- 2- (2-pyridyl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (2- (2-pyridyl) ethenyl) -1-oxa- 5,5,9,13- tetramethyl-7- (but-3-in-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (2- (2nd - pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-13-ethyl-16- (1-methyl-2- (2-pyridyl) ethenyl) -1-oxa- 5,5,9-trimethyl-7- (but-3-in-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-16-ethyl-10- (but-3-in-1-yl) - 3- ( 1-methyl-2- (2-pyridyl) ethenyl) -8,8,12-trimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-methyl- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (2- (2-pyridyl) ethenyl) -1-oxa- 5,5,9,13- tetramethyl-7- (but-3-in-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (2- (2nd - pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-fluoro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1- chloro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1-methyl- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (2- (2-pyridyl) ethenyl) -1-oxa- 5,5,9,13- tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (2- (2nd - pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1- fluoro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1- chloro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-methyl -2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-pyridyl) ethenyl) -1-oxa- 5,5,9 , 13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (2- ( 2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-fluor -2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-pyridyl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-chloro -2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1-methyl- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (2- (2-pyridyl) ethenyl) -1-oxa- 5,5,9,13- tetramethyl-7- (prop-2-in-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (2- (2nd -pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- fluoro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- chloro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1-methyl- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (2- (2-pyridyl) ethenyl) -1-oxa- 5,5,9,13- tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (2- (2nd -pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- fluoro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-pyridyl) ethenyl) -1-oxa-5.5, 9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- chloro- 2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-methyl-2- (2- pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-pyridyl) ethenyl) -1-oxa- 5,5,9 , 13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (2- (2-pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-fluoro-2- (2- pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-pyridyl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-chloro-2- (2- pyridyl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-methyl- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methylthiazol-4-yl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (2- (2nd - methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-fluoro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1- chloro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1-methyl- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methylthiazol-4-yl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (2- (2nd - methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1- fluoro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1- chloro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione (4S, 7R (RS), 8S , 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-
methylthiazol-4-yl) ethenyl) -1-oxa-5,5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-methyl -2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methylthiazol-4-yl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (2- ( 2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-fluor -2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methylthiazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-chloro -2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1-methyl- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methylthiazol-4-yl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (2- (2nd -methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- fluoro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- chloro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1-methyl- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methylthiazol-4-yl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (2- (2nd -methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- fluoro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-chloro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- chloro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-methyl-2- (2-methylthiazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-methyl-2- (2- methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methylthiazol-4-yl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (2- (2-methylthiazole-4- yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-fluoro-2- (2- methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methylthiazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-chloro-2- (2- methylthiazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-methyl- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methyloxazol-4-yl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (2- (2nd - methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-fluoro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1- chloro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1-methyl- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methyloxazol-4-yl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (2- (2nd - methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1- fluoro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (but-3-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-en-1-yl) -3- (1- chloro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-methyl-2- (2-methyloxazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-methyl -2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methyloxazol-4-yl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (2- ( 2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methyloxazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-fluor -2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methyloxazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (2-oxacyclopropyl-1-ethyl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (2-oxacyclopropyl-1-ethyl) -3- (1-chloro -2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1-methyl- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methyloxazol-4-yl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (2- (2nd -methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- fluoro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- chloro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1-methyl- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methyloxazol-4-yl) ethenyl) - 1-oxa-5,5, 9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (2- (2nd -methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- fluoro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5,9,13-tetramethyl-7- (prop-2-en-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- chloro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-methyl-2- (2-methyloxazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-methyl-2- (2- methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methyloxazol-4-yl) ethenyl) -1-oxa-5 , 5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (2- (2-methyloxazole-4- yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methyloxazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-fluoro-2- (2- methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methyloxazol-4-yl) ethenyl) -1 -oxa-5,5,9,13-tetramethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-chloro-2- (2- methyloxazol-4-yl) ethenyl) -8,8,12,16-tetramethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-methyl-2- (2-pyridyl) ethenyl) - 1-oxa-5,5- trimethylene-9,13-dimethyl-7- (but-3-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (but-3-in-1-yl) -3- (1-methyl- 2- (2-pyridyl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5,5- trimethylene-9,13-dimethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- fluoro- 2- (2-pyridyl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5,5- trimethylene-9,13-dimethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- fluoro- 2- (2-pyridyl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-pyridyl) ethenyl) -1-oxa-5 , 5-trimethylene-9,13-dimethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-fluoro-2- (2- pyridyl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5-trimethylene-9,13-dimethyl-7- (prop-2-in-1-yl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1-methyl- 2- (2-methylthiazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1-oxa- 5,5-trimethylene-9,13-dimethyl-7- (prop-2-in-1-yl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- fluoro- 2- (2-methylthiazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methylthiazol-4-yl) ethenyl) - 1-oxa-5,5- trimethylene-9,13-dimethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (2- (2nd -methylthiazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-fluoro-2- (2-methylthiazol-4-yl) ethenyl) -1 -oxa-5,5-trimethylene-9,13-dimethyl-7- (oxacyclopropylmethyl) - cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-fluoro-2- (2- methylthiazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methyloxazol-4-yl) ethenyl) - 1-oxa-5,5- trimethylene-9,13-dimethyl-7- (prop-2-yn-1-yl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (2- (2nd -methyloxazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5-trimethylene-9,13-dimethyl-7- (prop-2-in-1-yl) -cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-in-1-yl) -3- (1- fluoro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-methyl-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5-trimethylene-9,13-dimethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1-methyl- 2- (2-methyloxazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R, 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (1-fluoro-2- (2-methyloxazol-4-yl) ethenyl) -1-oxa- 5,5-trimethylene-9,13-dimethyl-7- (prop-2-en-1-yl) cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R, 11R, 12S, 16R / S) -7,11-dihydroxy-10- (prop-2-en-1-yl) -3- (1- fluoro- 2- (2-methyloxazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-dihydroxy-16- (2- (2-methyloxazol-4-yl) ethenyl) -1-oxa-5 , 5-trimethylene-9,13-dimethyl-7- (oxacyclopropylmethyl) cyclohexadec-13-ene-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (2- (2-methyloxazole-4- yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecane-5,9-dione
(4S, 7R (RS), 8S, 9S, 13E / Z, 16S (E)) - 4,8-Dihydroxy-16- (1-chloro-2- (2-methyloxazol-4-yl) ethenyl) -1 -oxa-5,5-trimethylene-9,13-dimethyl-7- (oxacyclopropylmethyl) - cyclohexadec-13-en-2,6-dione
(1S / R, 3S (E), 7S, 10R (RS), 11R, 12S, 16R / S) -7,11-dihydroxy-10- (oxacyclopropylmethyl) -3- (1-chloro-2- (2- methyloxazol-4-yl) ethenyl) -8,8-trimethylene-12,16-dimethyl-4,17-dioxabicyclo [14.1.0] heptadecan-5,9-dione. 7. Pharmazeutische Präparate, enthaltend mindestens eine Verbindung der allgemeinen Formel I gemäß Anspruch 1 sowie einen pharmazeutisch verträglichen Träger. 7. Pharmaceutical preparations containing at least one compound of general formula I according to claim 1 and a pharmaceutical compatible carrier.   8. Verwendung der Verbindungen der allgemeinen Formel I gemäß Anspruch 1 zur Herstellung von Arzneimitteln.8. Use of the compounds of general formula I according to Claim 1 for the manufacture of pharmaceuticals.
DE19954228A 1999-04-30 1999-11-04 New epothilone derivatives used for treating e.g. malignant melanoma, breast carcinoma, psoriasis, multiple sclerosis and arthritis Ceased DE19954228A1 (en)

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Application Number Priority Date Filing Date Title
DE19954228A DE19954228A1 (en) 1999-11-04 1999-11-04 New epothilone derivatives used for treating e.g. malignant melanoma, breast carcinoma, psoriasis, multiple sclerosis and arthritis
UA2001107395A UA73118C2 (en) 1999-11-04 2000-01-05 Derivatives of 6-alkenyl, 6-alkinyl and 6-epoxyepothilone, method for obtaining thereof and use in pharmaceutic preparates
PE2000000403A PE20010116A1 (en) 1999-04-30 2000-04-28 6-ALKENYL-, 6-ALKINYL- AND 6-EPOXY-EPOTILONE DERIVATIVES, PROCEDURES FOR THEIR PREPARATION
ARP000102024A AR023792A1 (en) 1999-04-30 2000-04-28 DERIVATIVES 6-ALQUENILO- AND 6-ALQUINILO-EPOTILONA, THE PROCEDURES TO PREPARE THEM AND THEIR USE IN PHARMACEUTICAL PRODUCTS
PCT/IB2000/000657 WO2000066589A1 (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
SI200031044T SI1173441T1 (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
JP2000615619A JP4024003B2 (en) 1999-04-30 2000-05-01 6-Alkenyl-, 6-alkynyl- and 6-epoxy-epothilone derivatives, methods for their production and their use in pharmaceutical formulations
DK00922826T DK1173441T3 (en) 1999-04-30 2000-05-01 6-alkenyl, 6-alkynyl and 6-epoxy-epothilone derivatives, processes for their preparation and their use in pharmaceutical compositions
CNB008069786A CN100368415C (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkinyl-and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
PL351491A PL210762B1 (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
CZ20013885A CZ299653B6 (en) 1999-04-30 2000-05-01 6-Alkenyl-, 6-alkynyl- and 6-epoxyepothilone derivatives, process of their preparation and pharmaceutical compositions in which the derivatives are comprised
NZ514989A NZ514989A (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkynyl- and 6-epoxy -epothilone derivatives
KR1020017013840A KR100721488B1 (en) 1999-04-30 2000-05-01 6-Alkenyl-, 6-Alkinyl- and 6-Epoxy-Epothilone Derivatives, Process for Their Production and Their Use in Pharmaceutical Preparations
AT00922826T ATE440847T1 (en) 1999-04-30 2000-05-01 6-ALKENYL, 6-ALKYNYL AND 6-EPOXY-EPOTHILONE DERIVATIVES. METHOD FOR THEIR PRODUCTION AND THEIR USE IN PHARMACEUTICAL COMPOSITIONS
CA2371226A CA2371226C (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
CA2651653A CA2651653C (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
SK1551-2001A SK286858B6 (en) 1999-04-30 2000-05-01 6-Alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
PT00922826T PT1173441E (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
EA200101025A EA011502B1 (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production and their use in pharmaceutical preparations
DE60042821T DE60042821D1 (en) 1999-04-30 2000-05-01 6-ALKENYL, 6-ALKYNYL AND 6-EPOXY EPOTHILONE DERIVATIVES. PROCESS FOR THE PRODUCTION THEREOF AND THEIR USE IN PHARMACEUTICAL COMPOSITIONS
IL14593800A IL145938A0 (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkinyl-and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
BR0010190-7A BR0010190A (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkynyl- and 6-epoxy-epothilone derivatives, process for their preparation, and their use in pharmaceutical preparations
MEP-139/08A MEP13908A (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
AU43103/00A AU772750C (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
MXPA01011039A MXPA01011039A (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations.
YUP-776/01A RS51023B (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production,and their use in pharmaceutical preparations
EEP200100568A EE05292B1 (en) 1999-04-30 2000-05-01 6-Alken-1, 6-alk n-1 and 6-epoxy epothilone derivatives, their preparation and their use in pharmaceutical preparations
ES00922826T ES2331506T3 (en) 1999-04-30 2000-05-01 DERIVATIVES OF 6-ALQUENIL-, 6-ALQUINIL-, 6-EPOXI-EPOTILONE, PROCEDURE FOR ITS PRODUCTION, AND ITS USE IN PHARMACEUTICAL PREPARATIONS.
EP00922826A EP1173441B1 (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
US09/979,939 US7125893B1 (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
HU0201010A HUP0201010A3 (en) 1999-04-30 2000-05-01 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
TW095145399A TWI294292B (en) 1999-04-30 2000-05-18 Combination of epothilone derivatives
TW89108133A TWI280962B (en) 1999-04-30 2000-05-18 6-alkenyl-, 6-alkinyl-and 6-epoxy-epothilone derivatives process for their production and their use in pharmaceutical preparations
IL145938A IL145938A (en) 1999-04-30 2001-10-15 6-alkenyl-, 6-alkinyl-and 6-epoxy-epothilone derivatives, process for their production, pharmaceutical compositions containing them and intermediates therefor
BG106053A BG65601B1 (en) 1999-04-30 2001-10-26 6-alkenyl-, 6-alkynyl- and 6-epoxy-epothilone derivatives, process for their production and their use in pharmaceutical preparations
NO20015278A NO328149B1 (en) 1999-04-30 2001-10-29 Epoxy-epothilone compounds, process for their preparation, their use for the preparation of pharmaceutical compositions and the pharmaceutical compositions.
ZA200109859A ZA200109859B (en) 1999-04-30 2001-11-29 6-Alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations.
HR20010892A HRP20010892A2 (en) 1999-04-30 2001-11-30 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
HK02108204.3A HK1046681B (en) 1999-04-30 2002-11-13 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use
US10/965,802 US7645891B2 (en) 1999-04-30 2004-10-18 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
US11/214,988 US7700621B2 (en) 1999-04-30 2005-08-31 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations
JP2007104224A JP4886578B2 (en) 1999-04-30 2007-04-11 6-Alkenyl-, 6-alkynyl- and 6-epoxy-epothilone derivatives, methods for their production and their use in pharmaceutical formulations
CY20091101237T CY1109768T1 (en) 1999-04-30 2009-11-25 6-ALKENYL-, 6-ALKINYL- AND 6-EPOXY-PRODUCED PRODUCTS, PROCEDURE FOR THEIR PREPARATION, AND THEIR USE IN PHARMACEUTICAL PARAMETERS
US12/721,614 US20100168179A1 (en) 1999-04-30 2010-03-11 6-alkenyl-, 6-alkinyl- and 6-epoxy-epothilone derivatives, process for their production, and their use in pharmaceutical preparations

Applications Claiming Priority (1)

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DE19954228A DE19954228A1 (en) 1999-11-04 1999-11-04 New epothilone derivatives used for treating e.g. malignant melanoma, breast carcinoma, psoriasis, multiple sclerosis and arthritis

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7649006B2 (en) 2002-08-23 2010-01-19 Sloan-Kettering Institute For Cancer Research Synthesis of epothilones, intermediates thereto and analogues thereof
US7750164B2 (en) 1996-12-03 2010-07-06 Sloan-Kettering Institute For Cancer Research Synthesis of epothilones, intermediates thereto, analogues and uses thereof
US7875638B2 (en) 2002-08-23 2011-01-25 Sloan-Kettering Institute For Cancer Research Synthesis of epothilones, intermediates thereto, analogues and uses thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7750164B2 (en) 1996-12-03 2010-07-06 Sloan-Kettering Institute For Cancer Research Synthesis of epothilones, intermediates thereto, analogues and uses thereof
USRE41990E1 (en) 1996-12-03 2010-12-07 Sloan-Kettering Institute For Cancer Research Synthesis of epothilones, intermediates thereto, analogues and uses thereof
US8481575B2 (en) 1996-12-03 2013-07-09 Sloan-Kettering Institute For Cancer Research Synthesis of epothilones, intermediates thereto, analogues and uses thereof
US7649006B2 (en) 2002-08-23 2010-01-19 Sloan-Kettering Institute For Cancer Research Synthesis of epothilones, intermediates thereto and analogues thereof
US7759374B2 (en) 2002-08-23 2010-07-20 Sloan-Kettering Institute For Cancer Research Synthesis of epothilones, intermediates thereto and analogues thereof
US7875638B2 (en) 2002-08-23 2011-01-25 Sloan-Kettering Institute For Cancer Research Synthesis of epothilones, intermediates thereto, analogues and uses thereof
US8110590B2 (en) 2002-08-23 2012-02-07 Sloan-Kettering Institute For Cancer Research Synthesis of epothilones, intermediates thereto and analogues thereof
US8513429B2 (en) 2002-08-23 2013-08-20 Sloan-Kettering Insitute For Cancer Research Synthesis of epothilones, intermediates thereto and analogues thereof

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