CN103012498A - Chiral ferrocene tridentate ligand and preparation method thereof as well as application in asymmetric hydrogenation reaction catalysis - Google Patents

Chiral ferrocene tridentate ligand and preparation method thereof as well as application in asymmetric hydrogenation reaction catalysis Download PDF

Info

Publication number
CN103012498A
CN103012498A CN2013100070461A CN201310007046A CN103012498A CN 103012498 A CN103012498 A CN 103012498A CN 2013100070461 A CN2013100070461 A CN 2013100070461A CN 201310007046 A CN201310007046 A CN 201310007046A CN 103012498 A CN103012498 A CN 103012498A
Authority
CN
China
Prior art keywords
alkyl
compound
tridentate ligand
aryl
ferrocene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2013100070461A
Other languages
Chinese (zh)
Other versions
CN103012498B (en
Inventor
陈卫平
张生勇
程司堃
李晓晔
聂慧芳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fourth Military Medical University FMMU
Original Assignee
Fourth Military Medical University FMMU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fourth Military Medical University FMMU filed Critical Fourth Military Medical University FMMU
Priority to CN201310007046.1A priority Critical patent/CN103012498B/en
Publication of CN103012498A publication Critical patent/CN103012498A/en
Application granted granted Critical
Publication of CN103012498B publication Critical patent/CN103012498B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a ferrocene tridentate ligand which has planar chirality and carbon chirality and is shown in a structure general formula (I). In the formula (I), R1 is aryl or C1-C6 alkyl, R2 is C1-C6 alkyl, n is equal to 1-4, or R2 does not exist. The ferrocene tridentate ligand is synthesized by adopting the steps of carrying out coupling and acetic anhydride esterifying with R12PCl after lithiating by sec-butyl lithium by using chiral Ugi's amine as a raw material, and finally generating nucleophilic substitution with aminomethyl pyridine or substituted aminomethyl pyridine. The chiral ferrocene tridentate ligand disclosed by the invention has high catalysis activity; and an Ir complex catalyst has excellent three-dimensional selectivity and high catalysis activity when being used in asymmetric hydrogenation of prochiral ketone.

Description

Chiral ferrocene tridentate ligand and preparation method thereof and the application in catalysis asymmetry hydrogenation reaction
Technical field
The present invention relates to the synthetic of a class chipal compounds, be specifically related to the synthetic and application aspect prochiral ketone catalysis asymmetric hydrogenation that a class has the ferrocene tridentate ligand of face chirality and carbon chirality concurrently, belong to technical field of organic synthesis.
Background technology
The hydrogenation of the latent unsaturated substrate of chirality (ketone, imines, alkene etc.) of chiral ligand and transition metal complex catalyst catalysis is the important channel that obtains various chiral materials.The key of asymmetric catalysis is the design of catalyzer of high reactivity and highly-solid selectively and synthetic, and chiral ligand is the root of chiral catalyst asymmetric induction and zinc bromide.In recent decades, people have designed and synthesized the part of many high catalytic activities and highly-solid selectively, and what have is applied to suitability for industrialized production.Such as DIOP (Kagan, H. B.; Dang, T. P. Chem. Commun. 1971, 481), BINAP (Yasuda, A.; Tayaka, H.; Miyashita, A.; Toriumi, K.; Ito, T.; Souchi T.; Noyori R. J. Am. Chem. Soc. 1980, 102,7932), DuPHOS (Burk, M. J.; Feaster, J. E.; Harlow, R. L. Organometallics. 1990, 9,2653), [(( S)-Tol-BINAP) (( S, S)-DEPEN)] (Noyori, R. Angew. Chem. Int. Ed. 1998, 37,1703) etc.Chiral ferrocene ligands iridium catalyst Ir-Xyliphos (Blaser, H. U. Adv. Synth. Catal. 2002, 344,17) and the asymmetric hydrogenation TON value of catalysis imines is up to 10 6, Zhou Qilin seminar of Nankai University report volution tridentate ligand iridium catalyst Ir-SpiroPAP (Xie, J. H.; Liu, X. Y.; Xie, J. B.; Wang, L. X.; Zhou, Q. L. Angew. Chem. Int. Ed. 2011, 50,7329) and TON value in the asymmetric hydrogenation of catalysis ketone is up to 4.5 * 10 6Although asymmetric catalytic hydrogenation research has obtained many achievements that attract people's attention in recent decades, but the catalyzer of catalytic activity high (the TON value reaches 1,000,000) is still very few, thereby more efficient and practical new chiral ligand and the catalyzer of design and development remains the important content that asymmetric synthesis is studied.
Summary of the invention
The object of the present invention is to provide that a class synthesis step is easy, the ferrocene tridentate ligand of the face that has concurrently the chirality of good stability and carbon chirality, the structure of this class part is based on Ir-Xyliphos and Ir-SpiroPAP chiral ligand structure activity study, has introduced the ferrocene structural unit of novel face chirality in structure.
Another object of the present invention is to provide the preparation method of above-mentioned chiral ligand.
A further object of the invention is to provide the application of iridium complex catalyzer in the asymmetric catalytic hydrogenation of prochiral ketone of above-mentioned tridentate ligand.
Implementation procedure of the present invention is as follows:
General structure ( I) shown in the ferrocene tridentate ligand:
Figure 569348DEST_PATH_IMAGE001
Wherein, R 1Be C 1～C 6Alkyl or aryl; R 2Be C 1～C 6Alkyl, n=1～4, or R 2Do not exist.
Described aryl refers to any from functional group or substituting group that simple aromatic nucleus derives, comprises phenyl that phenyl, C1-C5 alkyl replace, 1-naphthyl (or Alpha-Naphthyl), 2-naphthyl etc.
General structure ( I) be RThe carbon chirality and SFace chiral tridentate part, or SThe carbon chirality and RFace chiral tridentate part, or racemic tridentate ligand.
The preparation method of above-mentioned ferrocene tridentate ligand comprises the steps: take chirality Ugi ' s amine as raw material after the s-butyl lithium lithiumation and R 1 2PCl coupling, aceticanhydride esterification, last and aminomethyl-pyridine or pyridine ring are by R 2The aminomethyl-pyridine generation nucleophilic substitution reaction that replaces is synthetic to obtain R 1Be the alkyl of aryl or C1～C6, R 2Alkyl for C1～C6.
The present invention also include general structure ( I) shown in the complex of iridium of ferrocene tridentate ligand.
Ferrocene tridentate ligand of the present invention is applied in the prochiral ketone catalysis asymmetric hydrogenation, specifically, the present invention with chirality Ugi ' s amine ( A) be starting raw material, at first after the s-butyl lithium lithiumation with R 1 2The PCl reaction obtained product in 1～5 hour B, temperature of reaction-20～50 ℃, reaction solvent is methyl tertiary butyl ether; Then in aceticanhydride, stir and obtained in 1～24 hour C, 0～150 ℃ of temperature of reaction; Last in the mixed solvent of methyl alcohol and tetrahydrofuran (THF) with the aminomethyl-pyridine reaction of aminomethyl-pyridine or replacement obtained in 1～24 hour part ( I), 0～100 ℃ of temperature of reaction.
Figure 486488DEST_PATH_IMAGE002
Chiral ferrocene ligands of the present invention has face chirality and carbon chirality simultaneously, its comprise from RThe synthetic face chirality of configuration Ugi ' s amine is SConfiguration ( R, S)-part and from SConfiguration Ugi ' s amine synthetic ( S, R)-part.The part of isomorphism type does not have identical chemical structure of general formula, but has different three-dimensional arrangements and opticity.
Chiral ferrocene ligands of the present invention is to have the very part of high catalytic activity, its Ir complex compound catalyst has outstanding stereoselectivity and very high catalytic activity when being used for the asymmetric hydrogenation of prochiral ketone, the mol ratio of prochiral ketone and chiral ligand (I) is 1000～1000000,0～60 ℃ of temperature of reaction, hydrogen pressure is 1～150atm, reaction times is 1～48h, and reaction solvent is the alcohol organic solvent such as methyl alcohol, its reaction expression:
Figure 266225DEST_PATH_IMAGE003
R 1Be C 1～C 6Alkyl or aryl; N=0～4, R 2Be C 1～C 6Alkyl; R 3, R 4Be independently selected from C 1～C 6Alkyl, cycloalkyl or aryl, R 3, R 4Not identical.
Chiral ferrocene ligands of the present invention has very high catalytic activity, and its Ir complex compound catalyst has outstanding stereoselectivity and very high catalytic activity when being used for the asymmetric hydrogenation of prochiral ketone.
Embodiment
Embodiment 1 synthetic ( R C , S Fe )-1-[(2-biphenyl phosphino-) ferrocenyl]- N, N-dimethyl amine
Figure 723751DEST_PATH_IMAGE004
Take by weighing ( R)-Ugi ' s amine (2.57 g, 10 mmol) adds in the Schlenk reaction tubes of 50 mL, vacuumizes/inflated with nitrogen three times, injects dry methyl tertiary butyl ether 15 mL that cross, and is stirred to dissolving, slowly injects 1.3 M s-BuLi (9.2 mL, 12 mmol), react at ambient temperature 1 hour generation orange floss, slowly inject again diphenyl phosphine chloride (1.8 mL that are dissolved in 10 mL methyl tertiary butyl ethers, 10 mmol), temperature rise to 40 ℃ the reaction 4 hours to reacting completely.Remove by filter insolubles, column chromatography gets product 3.1 g after the solvent evaporated, with dehydrated alcohol recrystallization 1.8 g, productive rate 40.8%.
mp?141-143℃;?
Figure 538124DEST_PATH_IMAGE005
?-350.9?(c?=?0.25,?CHCl 3);? 1H?NMR?(500?Hz,?CDCl 3)：δ?7.62-7.56?(m,?2H),?7.37-7.32?(m,?3H),?7.22-7.14?(m,?5H),?4.37?(s,?1H),?4.25-4.24?(m,?1H),?4.16-4.14?(dd,? J 1 =?2.5,? J 2? =2.5?Hz,?1H),?3.94?(s,?5H),?3.86?(s,?1H),?1.77?(s,?6H),?1.27-1.26?(d,?J?=?7?Hz,?3H).
Embodiment 2 synthetic ( R C , S Fe )-1-[2-two (3,5-3,5-dimethylphenyl) phosphino-] ferrocenyl- N, N-dimethyl amine
Figure 921438DEST_PATH_IMAGE006
The preparation method gets orange oily matter 2.2 g, productive rate 44.2% with embodiment 1.
?-278.5?(c?=?0.25,?CHCl 3);? 1H?NMR?(500?Hz,?CDCl 3)?δ?7.25-7.23?(m,?2H),?6.98?(s,?1H),?6.80-6.78?(m,?3H),?4.35?(s,?1H),?4.23-4.22?(m,?1H),?4.10-4.08?(dd,? J 1 =?2.5,? J 2 =2.5?Hz,?1H),?3.92?(s,?5H),?3.87?(s,?1H),?2.32?(s,?6H),?2.18?(s,?6H),?1.81?(s,?6H),?1.28-1.27?(d,?J?=?7?Hz,?3H).
Embodiment 3 synthetic ligands ( R C , S Fe )-1-(2-diphenylphosphino) ferrocenyl)- N-(pyridyl-2-methyl) ethamine
Take by weighing ( R)- N, N-dimethyl-1-[( S)-2-(diphenylphosphino) ferrocenyl] ethamine (0.882 g, 2 mmol) adds in the 50 mL Schlenk reaction tubess, vacuumizes/inflated with nitrogen three times, injects 15 mL aceticanhydrides, and stirring at ambient temperature spends the night to reaction finishes.Decompression is with the solvent evaporate to dryness, and gained acetic ester solid product directly carries out the next step.Above-mentioned gained solid is added in the 50 mL there-necked flasks, and the mixing solutions (1:1) that adds first 10 mL methyl alcohol and tetrahydrofuran (THF) is stirred to dissolve complete, adds 0.5 mL 2-aminomethyl-pyridine again, and back flow reaction 10 hours is to reacting completely.Be spin-dried for behind extracted with diethyl ether, the anhydrous sodium sulfate drying after the frozen water cancellation, column chromatography gets product 0.51 g, productive rate 47.2%.
m.p.?137.2～139.5?℃， 1H?NMR?(400?MHz,?CDCl 3) ,δ8.34-8.13(d, ?J=4.4Hz,?1H),7.48-7.40(m,3H),7.39-6.80(m,9H),6.62-6.45(d, ?J=7.6Hz,?1H),4.52-4.50(s,1H),4.35-4.25(s,?1H),?4.25-4.15?(dd,? J 1 =2.4Hz,? J 2 =2.4Hz,?1H),4.15-3.90(s,5H),?3.85-3.77?(s,?1H),?3.70-3.55(d,? J=2Hz,?2H),?2.00-2.10(s,?1H),?1.65-1.50(d,? J=6.4Hz,?3H).
Embodiment 4 synthetic ligands ( R C , S Fe )-1-(2-diphenylphosphino) ferrocenyl)- N-(quinolyl-2-methyl) ethamine
Figure 118567DEST_PATH_IMAGE008
The preparation method gets yellow blister solid 0.59 g, productive rate 53.2% with embodiment 3.
Figure 174248DEST_PATH_IMAGE005
?-276.8?(c?=?0.25,?CH 2Cl 2);? 1H?NMR?(500?Hz,?CDCl 3)?δ7.93-7.85?(d,? J?=?8.5?Hz,?1H),?7.84-7.78?(d, ?J?=?8.5?Hz,?1H),?7.74-7.67?(d,? J?=?8?Hz,?1H),?7.65-7.59?(m,?1H),?7.58-7.51?(m,?2H),?7.49-7.42?(m,?1H),?7.40-7.33?(m,?3H),?7.25-7.20?(m,?1H),?7.14-7.06?(m,?2H),?7.03-6.98?(m,?1H),?6.79-6.74?(d,? J?=?8.5?Hz,?1H),?4.58?(s,?1H),?4.34?(s,?1H),?4.33-4.25?(d,? J?=?3.5?Hz,?1H),?4.01?(s,?5H),?3.90-3.80(m,?3H),?1.65-1.58?(d,? J?=?6?Hz,?3H).
Embodiment 5 synthetic ligands ( R C , S Fe )-1-(2-diphenylphosphino) ferrocenyl)- N-(3-pyridyl-2-methyl) ethamine
Figure 928577DEST_PATH_IMAGE009
The preparation method gets orange solid 0.62 g, productive rate 60.1% with embodiment 3.
mp?103.2-104℃;?
Figure 665589DEST_PATH_IMAGE005
?-353.6?(c?=?0.25,?CH 2Cl 2);? 1H?NMR?(500?Hz,?CDCl 3)?δ?8.10-8.05?(d,? J?=?4?Hz,?1H),?7.60-7.52?(m,?2H),?7.40-7.32?(m,?3H),?7.23-7.16?(m,?3H),?7.13-7.03?(m,?3H),?6.92-6.87?(m,?1H),?4.57?(s,?1H),?4.33-.4.30?(m,?1H),?4.18-4.12?(dd,? J 1 =3, ?J 2 =2.5?Hz,?1H),?3.97?(s,?5H),?3.88-3.84?(m,?1H),?3.78-3.63?(d, ?J?=?14?Hz,?1H),?3.54-3.49?(d,? J?=?14?Hz,?1H),?1.97?(s,?3H),?1.66?-1.61?(d,? J?=?6.5?Hz,?3H).
Embodiment 6 synthetic ligands ( R C , S Fe )-1-(2-diphenylphosphino) ferrocenyl)- N-(6-pyridyl-2-methyl) ethamine
The preparation method gets sticky solid 0.65 g of orange, productive rate 63.2% with embodiment 3.
Figure 681136DEST_PATH_IMAGE005
?-243.8?(c?=?0.65,?CH 2Cl 2);? 1H?NMR?(500?Hz,?CDCl 3)?δ?7.56-7.50?(m,?2H),?7.40-7.33?(m,?3H),?7.28-7.20?(m,?3H),?7.17-7.10?(m,?3H),?6.88-6.82?(d,? J?=?7.5?Hz,?1H),?6.36-6.30?(d,? J?=?7.5?Hz,?1H),?4.53?(s,?1H),?4.33-4.28?(m,?1H),?4.25-4.17?(m,?1H),?4.00?(s,?5H),?3.85-3.80?(m,?1H),?3.62?(s,?1H),?2.41?(s,?3H),?1.57-1.53?(d,? J?=?6.5?Hz,?3H).
Embodiment 7 synthetic ligands ( R C , S Fe )-1-[2-(two (3,5-3,5-dimethylphenyl) phosphino-) ferrocenyl]- N-(6-pyridyl-2-methyl) ethamine
The preparation method gets sticky solid 0.52 g of orange, productive rate 45.5% with embodiment 3.
Figure 197885DEST_PATH_IMAGE005
?-262.4?(c?=?0.25,?CH 2Cl 2);? 1H?NMR?(500?Hz,?CDCl 3)?δ?7.28-7.23?(m,?1H),?7.22-7.17?(d,? J?=?8.5?Hz,?2H),?7.04?(s,?1H),?6.92-6.84?(m,?3H),?6.74?(s,?1H),?6.32-6.28?(d,? J?=?8?Hz,?1H),?4.55?(s,?1H),?4.34-4.30?(m,?1H),?4.29-4.22?(dd,? J?=?3,?3?Hz,?1H),?4.08?(s,?5H),?3.87-3.82?(m,?1H),?3.68-3.58?(dd,? J?=?14.5,?14.5?Hz,?2H),?2.47?(s,?3H),?2.35?(s,?6H),?2.11?(s,?6H),?1.61-1.56?(d, ?J?=?6.5?Hz,?3H).
The asymmetric hydrogenation of embodiment 8 prochiral ketones
Figure 405137DEST_PATH_IMAGE012
R 1Be C 1～C 6Alkyl or aryl; N=0～4, R 2Be C 1～C 6Alkyl; R 3, R 4Be independently selected from C 1～C 6Alkyl, cycloalkyl or aryl, R 3, R 4Not identical.
Take by weighing part ( R C, S Fe)-1-[2-(two (3,5-3,5-dimethylphenyl) phosphino-) ferrocenyl]- N-(6-pyridyl-2-methyl) ethamine (12.6 mg, 0.022 mmol), [Ir (COD) Cl] 2(7.32 mg, 1 mmol) adds in the 25 mL Schlenk reaction tubess, vacuumizes/inflated with nitrogen three times, injects 2 mL through the dehydrated alcohol of nitrogen replacement, and stirring at room 1 hour is for subsequent use.With methyl phenyl ketone (4.8 g, 40 mmol) add in the 100 mL autoclaves, add 30 mL through the dehydrated alcohol of nitrogen replacement, again above-mentioned reaction solution is added in the reactor, behind the hydrogen exchange three times, pressure is risen to 20 atm, stirred 24 hours under the room temperature, TLC shows and to react completely, column chromatography obtain the weak yellow liquid product ( R)-1-phenylethyl alcohol 2.2 g, productive rate 90.9%, EeValue 78%.

Claims (8)

  1. General structure ( I) shown in compound:
    Figure 320832DEST_PATH_IMAGE001
    Wherein, R 1Be aryl or C 1～C 6Alkyl; R 2Be C 1～C 6Alkyl, n=1～4, or R 2Do not exist.
  2. 2. ferrocene tridentate ligand according to claim 1 is characterized in that: general structure ( I) shown in compound be RThe carbon chirality and SFace chiral tridentate part, or SThe carbon chirality and RFace chiral tridentate part, or racemic tridentate ligand.
  3. 3. the preparation method of the described compound of claim 1 is characterized in that comprising the steps: take chirality Ugi ' s amine as raw material after the s-butyl lithium lithiumation and R 1 2PCl coupling, aceticanhydride esterification, last and aminomethyl-pyridine or pyridine ring are by R 2The aminomethyl-pyridine generation nucleophilic substitution reaction that replaces is synthetic to be obtained, and reaction formula is as follows,
    Figure 595956DEST_PATH_IMAGE002
    R 1Be the alkyl of aryl or C1～C6, R 2Alkyl for C1～C6.
  4. 4. the complex of iridium that contains the described compound of claim 1.
  5. 5. the application of the described compound of claim 1 in prochiral ketone catalysis asymmetric hydrogenation.
  6. 6. according to claim 5 described application is characterized in that: general structure ( I) shown in compound and transition metal iridium original position generate the hydrogenation that is used for the catalysis prochiral ketone after the metal complex catalyst.
  7. 7. according to claim 6 described application is characterized in that: prochiral ketone and general structure ( I) shown in the mol ratio of compound be 1000～1000000,0～60 ℃ of temperature of reaction, hydrogen pressure is 1～150atm, the reaction times is 1～48h.
  8. 8. according to claim 7 described application is characterized in that the catalyzed reaction formula is as follows:
    R 1Be aryl or C 1～C 6Alkyl; N=0～4, R 2Be C 1～C 6Alkyl, n=1～4, or R 2Do not exist; R 3, R 4Be independently selected from C 1～C 6Alkyl, cycloalkyl or aryl, R 3, R 4Not identical.
CN201310007046.1A 2012-01-10 2013-01-09 Chiral ferrocene tridentate ligand and preparation method thereof and the application in catalysis asymmetry hydrogenation reaction Expired - Fee Related CN103012498B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310007046.1A CN103012498B (en) 2012-01-10 2013-01-09 Chiral ferrocene tridentate ligand and preparation method thereof and the application in catalysis asymmetry hydrogenation reaction

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN201210005927 2012-01-10
CN201210005927.5 2012-01-10
CN201310007046.1A CN103012498B (en) 2012-01-10 2013-01-09 Chiral ferrocene tridentate ligand and preparation method thereof and the application in catalysis asymmetry hydrogenation reaction

Publications (2)

Publication Number Publication Date
CN103012498A true CN103012498A (en) 2013-04-03
CN103012498B CN103012498B (en) 2016-01-13

Family

ID=47961647

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310007046.1A Expired - Fee Related CN103012498B (en) 2012-01-10 2013-01-09 Chiral ferrocene tridentate ligand and preparation method thereof and the application in catalysis asymmetry hydrogenation reaction

Country Status (1)

Country Link
CN (1) CN103012498B (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103288768A (en) * 2013-06-18 2013-09-11 中国人民解放军第四军医大学 Asymmetric synthetic method of optical pure amorolfine hydrochloride
CN103831132A (en) * 2014-02-25 2014-06-04 中国人民解放军第四军医大学 Double-function square amide-phosphine organic catalyst based on ferrocene skeleton, preparation method and application of catalyst
CN103831133A (en) * 2014-02-25 2014-06-04 中国人民解放军第四军医大学 Bi-functional phosphine thiourea organic catalyst based on ferrocene skeleton as well as preparation method and application thereof
CN104592313A (en) * 2014-12-30 2015-05-06 陕西师范大学 Double functional hydrogen bond organic catalyst based on ferrocene as well as preparation method and application of double functional hydrogen bond organic catalyst
CN105153229A (en) * 2015-06-18 2015-12-16 武汉凯特立斯科技有限公司 Chiral tridentate PNN ligand and application of same in asymmetric hydrogenation
CN105732725A (en) * 2016-01-30 2016-07-06 武汉凯特立斯科技有限公司 Chiral tridentate nitrogen-phosphine-oxygen ligands and application of related ligands in asymmetric catalytic reactions
CN107522751A (en) * 2016-06-21 2017-12-29 中国科学院大连化学物理研究所 A kind of high steric-hindrance amino chiral ferrocene P, N, N part and preparation method and application
CN108101785A (en) * 2016-11-24 2018-06-01 中国科学院大连化学物理研究所 A kind of method that iridium catalysis asymmetric hydrogenation prepares chiral beta-hydroxy ester
CN110183498A (en) * 2019-06-17 2019-08-30 浙江工业大学 A kind of chiral ferrocene phosphine nitrogen nitrogen tridentate ligand and its preparation method and application
CN112300220A (en) * 2020-11-11 2021-02-02 武汉纺织大学 Chiral ferrocene P, N ligand derivative and preparation method and application thereof
CN113004341A (en) * 2021-03-08 2021-06-22 洛阳师范学院 PNO ligand containing chiral ferrocene and axial chiral biphenol and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6034240A (en) * 1998-03-09 2000-03-07 Symyx Technologies, Inc. Substituted aminomethylphosphines, coordination complexes of aminomethylphosphines and their synthesis
CN101010327A (en) * 2004-05-04 2007-08-01 乌迪内大学 Complexes of ruthenium with 2-(aminomethyl) pyridines and phosphines, their preparation and use as catalysts

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6034240A (en) * 1998-03-09 2000-03-07 Symyx Technologies, Inc. Substituted aminomethylphosphines, coordination complexes of aminomethylphosphines and their synthesis
CN101010327A (en) * 2004-05-04 2007-08-01 乌迪内大学 Complexes of ruthenium with 2-(aminomethyl) pyridines and phosphines, their preparation and use as catalysts

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JIAN-HUA XIE ET AL: "An Additional Coordination Group Leads to Extremely Efficient Chiral Iridium Catalysts for Asymmetric Hydrogenation of Ketones", 《ANGEW. CHEM. INT. ED.》, vol. 50, no. 32, 12 July 2011 (2011-07-12), pages 7329 - 7332 *
PATTUBALA A. N. REDDY ET AL: "2,6-Bis({rac-1-[2-(diphenylphosphino)ferrocenyl]ethyl}aminocarbonyl)pyridine", 《ACTA CRYSTALLOGRAPHICA SECTION E》, vol. 63, no. 4, 7 March 2007 (2007-03-07), pages 971 - 972 *
WEIPING CHEN ET AL: "A Very Simple, Highly Stereoselective and Modular Synthesis of Ferrocene-Based P-Chiral Phosphine Ligands", 《J. AM. CHEM. SOC.》, vol. 128, no. 12, 8 March 2006 (2006-03-08), pages 3922 - 3923 *
WEIPING CHEN ET AL: "Ferrocene-based aminophosphine ligands in the Ru(II)-catalysed asymmetric hydrogenation of ketones: assessment of the relative importance of planar versus carbon-centred chirality", 《TETRAHEDRON: ASYMMETRY》, vol. 17, no. 8, 24 May 2006 (2006-05-24) *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103288768A (en) * 2013-06-18 2013-09-11 中国人民解放军第四军医大学 Asymmetric synthetic method of optical pure amorolfine hydrochloride
CN103831132A (en) * 2014-02-25 2014-06-04 中国人民解放军第四军医大学 Double-function square amide-phosphine organic catalyst based on ferrocene skeleton, preparation method and application of catalyst
CN103831133A (en) * 2014-02-25 2014-06-04 中国人民解放军第四军医大学 Bi-functional phosphine thiourea organic catalyst based on ferrocene skeleton as well as preparation method and application thereof
CN104592313A (en) * 2014-12-30 2015-05-06 陕西师范大学 Double functional hydrogen bond organic catalyst based on ferrocene as well as preparation method and application of double functional hydrogen bond organic catalyst
CN104592313B (en) * 2014-12-30 2017-08-25 陕西师范大学 Difunctional hydrogen bond organic catalyst based on ferrocene and its preparation method and application
CN105153229A (en) * 2015-06-18 2015-12-16 武汉凯特立斯科技有限公司 Chiral tridentate PNN ligand and application of same in asymmetric hydrogenation
CN105732725A (en) * 2016-01-30 2016-07-06 武汉凯特立斯科技有限公司 Chiral tridentate nitrogen-phosphine-oxygen ligands and application of related ligands in asymmetric catalytic reactions
CN105732725B (en) * 2016-01-30 2019-05-24 武汉凯特立斯科技有限公司 A kind of application of chiral tridentate nitrogen phosphine oxygen ligand and its associated ligands in asymmetric catalysis
CN107522751B (en) * 2016-06-21 2020-01-21 中国科学院大连化学物理研究所 High-steric-hindrance chiral ferrocene P, N, N ligand, preparation method and application
CN107522751A (en) * 2016-06-21 2017-12-29 中国科学院大连化学物理研究所 A kind of high steric-hindrance amino chiral ferrocene P, N, N part and preparation method and application
CN108101785A (en) * 2016-11-24 2018-06-01 中国科学院大连化学物理研究所 A kind of method that iridium catalysis asymmetric hydrogenation prepares chiral beta-hydroxy ester
CN110183498A (en) * 2019-06-17 2019-08-30 浙江工业大学 A kind of chiral ferrocene phosphine nitrogen nitrogen tridentate ligand and its preparation method and application
CN110183498B (en) * 2019-06-17 2022-04-29 浙江工业大学 Chiral ferrocene phosphine nitrogen tridentate ligand and preparation method and application thereof
CN112300220A (en) * 2020-11-11 2021-02-02 武汉纺织大学 Chiral ferrocene P, N ligand derivative and preparation method and application thereof
CN112300220B (en) * 2020-11-11 2023-04-18 武汉纺织大学 Chiral ferrocene P, N ligand derivative and preparation method and application thereof
CN113004341A (en) * 2021-03-08 2021-06-22 洛阳师范学院 PNO ligand containing chiral ferrocene and axial chiral biphenol and application thereof
CN113004341B (en) * 2021-03-08 2023-08-01 洛阳师范学院 PNO ligand containing facial chiral ferrocene and axial chiral diphenol and application thereof

Also Published As

Publication number Publication date
CN103012498B (en) 2016-01-13

Similar Documents

Publication Publication Date Title
CN103012498B (en) Chiral ferrocene tridentate ligand and preparation method thereof and the application in catalysis asymmetry hydrogenation reaction
Chan et al. Development of ruthenium catalysts for the enantioselective synthesis of P-stereogenic phosphines via nucleophilic phosphido intermediates
EP2563799B1 (en) Ruthenium complex and method for preparing optically active alcohol compound
Aydemir et al. A modular design of ruthenium (II) catalysts with chiral C2-symmetric phosphinite ligands for effective asymmetric transfer hydrogenation of aromatic ketones
Zhou et al. Palladium-catalyzed asymmetric hydrogenation of simple ketones activated by Brønsted acids
Elma et al. Screening of C2-symmetric chiral phosphinites as ligands for ruthenium (II)-catalyzed asymmetric transfer hydrogenation of prochiral aromatic ketones
Aydemir et al. Asymmetric transfer hydrogenation of acetophenone derivatives with novel chiral phosphinite based η6-p-cymene/ruthenium (II) catalysts
CA2830481C (en) Ruthenium complex and method for preparing optically active alcohol compounds using the same as a catalyst
Imamoto et al. Utilization of optically active secondary phosphine–boranes: Synthesis of P-chiral diphosphines and their enantioinduction ability in rhodium-catalyzed asymmetric hydrogenation
CN105348321B (en) One kind synthesis α, the method for α difluoro methylene alkenyl phosphonates
Tanaka Asymmetric Synthesis of Axially Chiral Compounds by Rhodium (I)-Catalyzed [2+ 2+ 2] Cycloaddition
CN102391306B (en) Spirobenzylamine-phosphine and preparation method and application thereof
Durap et al. New C2-symmetric chiral phosphinite ligands based on amino alcohol scaffolds and their use in the ruthenium-catalysed asymmetric transfer hydrogenation of aromatic ketones
Zhao et al. Cu-catalyzed enantioselective conjugate addition of diethylzinc to cyclic enones with chiral phosphite ligands derived from 1, 2: 5, 6-di-O-cyclohexylidene-d-mannitol
US6207868B1 (en) Asymmetric synthesis catalyzed by transition metal complexes with chiral ligands
CN102675016A (en) Alpha-keto ester compound with gamma chiral center and synthetic method thereof
Braun et al. Chiral diphosphine ligands based on an arene chromium tricarbonyl scaffold: a modular approach to asymmetric hydrogenation
Meriç et al. New functional chiral P-based ligands and application in ruthenium-catalyzed enantioselective transfer hydrogenation of ketones
CN103665038B (en) A kind of carbon phosphorus chirality dialkyl phosphine oxide and synthetic method thereof
CN103831133A (en) Bi-functional phosphine thiourea organic catalyst based on ferrocene skeleton as well as preparation method and application thereof
Diéguez et al. Furanoside thioether–phosphinite ligands for Rh-catalyzed asymmetric hydrosilylation of ketones
Zhao et al. Enantioselective copper (II)-catalyzed conjugate addition of diethylzinc to β-substituted enones utilizing BINOL-based phosphoramidite ligands
Hu et al. Electronically deficient (Rax, S, S)-F12-C3-TunePhos and its applications in asymmetric 1, 4-addition reactions
Aydemir et al. Cationic and neutral ruthenium (II) complexes containing both arene or Cp* and functionalized aminophosphines. Application to hydrogenation of aromatic ketones
Hua et al. The synthesis and application of novel C2-symmetric chiral N, N, O, O bisoxazoline ligands with a ferrocene backbone

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160113

Termination date: 20170109