WO2009043303A1 - Procédé de stéréosélectivité dans une réaction de substitution allylique par catalyse au palladium - Google Patents

Procédé de stéréosélectivité dans une réaction de substitution allylique par catalyse au palladium Download PDF

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Publication number
WO2009043303A1
WO2009043303A1 PCT/CN2008/072561 CN2008072561W WO2009043303A1 WO 2009043303 A1 WO2009043303 A1 WO 2009043303A1 CN 2008072561 W CN2008072561 W CN 2008072561W WO 2009043303 A1 WO2009043303 A1 WO 2009043303A1
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Prior art keywords
group
substitution reaction
allyl
catalyzed
reaction according
Prior art date
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PCT/CN2008/072561
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English (en)
Chinese (zh)
Inventor
Wan Bin Zhang
Fang Xie
De Long Liu
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Shanghai Jiaotong University
Nippon Chemical Industrial Co.Ltd.
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Application filed by Shanghai Jiaotong University, Nippon Chemical Industrial Co.Ltd. filed Critical Shanghai Jiaotong University
Priority to CN200880108610A priority Critical patent/CN101808975A/zh
Publication of WO2009043303A1 publication Critical patent/WO2009043303A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
    • C07C211/28—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by unsaturated carbon chains
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/44—Allylic alkylation, amination, alkoxylation or analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
    • B01J2531/0263—Planar chiral ligands, e.g. derived from donor-substituted paracyclophanes and metallocenes or from substituted arenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

Definitions

  • the present invention relates to a process in the field of chemical engineering, and in particular to a stereoselective process for the preparation of a Pd-catalyzed allyl substitution reaction. Background technique
  • the stereoscopic factors of the ligand have a great influence on the absolute configuration and the size of the enantioselectivity of the product.
  • the common method is to synthesize two ligands with opposite configurations. Due to the asymmetry of nature itself, the chiral source of one configuration is often sufficient, but the other configuration is difficult to obtain, which makes the application of this method have great limitations. Therefore, chemists have been working to achieve enantioselective inversion by changing other factors while the original ligand configuration (chiral skeleton) is unchanged.
  • simple structural modification of the original chiral ligand is one of the more meaningful methods, and its operation is simple, and it is convenient to predict the stereo configuration of the product, and the screening range is wide.
  • the product of the invention has better predictability and simple operation.
  • the present invention has been achieved by the following technical solutions.
  • the present invention is characterized in that, in the reaction in which a transition metal complex compound is used as a catalyst, a substitution reaction of an olefin having a leaving group at a ally site with a nucleophilic reagent, and a stereoselectivity of an allylic site is used,
  • a transition metal complex compound a Pd transition metal complex compound having a bisphosphine compound as a ligand represented by the following general formula (1) or (2) is used.
  • R 1 represents a fluorenyl group having 1 to 4 carbon atoms or a group containing an amide functional group.
  • R 2 represents a hydrogen atom, a fluorenyl group having 1 to 4 carbon atoms or an acetyl group.
  • M represents an iron atom. Or helium atoms.
  • a Pd transition metal complex compound having a metallocene bisphosphine compound as a ligand in which M in the above formula is a halogen atom.
  • a Pd transition metal complex compound having a bisphosphine compound as a ligand of the above formula (1) can be used as a main product to obtain a compound having a stereo configuration of S type. Further, by using the Pd transition metal complex compound having the bisphosphine compound as the ligand of the above formula (2), a compound having a stereo configuration can be obtained as a main product.
  • the olefin is allyl acetate
  • the allylic acetate is preferably a compound represented by the formula (3).
  • R 3 and R 4 represent a fluorenyl group having a substituent or having no substituent, an aryl group having a substituent or having no substituent, and Ac represents an acetyl group.
  • the above allyl substitution reaction is an asymmetric allyl group thiolation reaction
  • the above nucleophilic reagent is preferably dimethyl malonate, further in an asymmetric allyl group.
  • the reaction it is preferred to carry out a reaction by adding N,S-bis(trimethylsilyl)acetamide and sodium acetate.
  • the allyl substitution reaction is an asymmetric allyl amination reaction
  • the nucleophilic reagent is preferably a benzylamine.
  • the bisphosphine ligand to be used as a ligand used in the present invention is a compound represented by the following formula (1) or (2).
  • R 1 in the above formula (1) represents a linear or branched fluorenyl group having 1 to 4 carbon atoms or a group having an amide functional group.
  • the thiol group include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • the amide functional group-containing group is represented by the formula: -CONRR', wherein R and R' represent a linear or branched fluorenyl group having 1 to 5 carbon atoms or a phenyl group.
  • R 1 in the formula (1) particularly preferably represents a linear or branched fluorenyl group having 1 to 4 carbon atoms.
  • R 2 in the above formula (2) represents a hydrogen atom, a linear or branched fluorenyl group having 1 to 4 carbon atoms or an acryloyl group.
  • the mercapto group include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • M in the above formula (1) or (2) represents an iron atom or a ruthenium atom, and among them, a ruthenium atom is particularly preferable.
  • the bisphosphine ligand represented by the above formula (1) or (2) is a known compound, and can be produced, for example, according to the following reaction mechanism (1) (refer to International Publication No. 2007/140717).
  • R 1 and M have the same meanings as defined above.
  • R 2 ' represents a fluorenyl group having a substituent or having no substituent, and Ac represents an acetyl group.
  • a halogenated allyl group or an allyl acetate is preferable, and an allyl acetate represented by the following formula (3) is particularly preferable.
  • R 3 and R 4 in the formula (3) represent a fluorenyl group having a substituent or having no substituent, an aryl group having a substituent or not having a substituent, and Ac represents an acetyl group.
  • mercapto group a linear or branched mercapto group having 1 to 8 carbon atoms is preferable.
  • aryl group a phenyl group, a tolyl group, a xylyl group or a naphthyl group is preferable.
  • examples of the substituent of the above mercapto group and the aryl group include an alcohol, an amine, a carboxylic acid, an ester, an amide, an ether, an acyl group, and a halogen group.
  • R 3 and R 4 are the same or different. In the present invention, R 3 and R 4 are particularly preferably a phenyl group.
  • the allyl substitution reaction of the present invention can be preferably used for an asymmetric allyl group thiolation reaction or an asymmetric allyl group amination reaction. Therefore, the nucleophilic test (J is preferably a dinonanol malonate represented by the following formula (4), and an amine compound represented by the following formula (5).
  • R 5 in the above formula (4) represents a fluorenyl group having a substituent or having no substituent.
  • a linear or branched mercapto group having 1 to 8 carbon atoms is preferable.
  • the substituent of the above mercapto group may, for example, be an alcohol, an amine, a carboxylic acid, an ester, an amide, an ether, an acyl group or a halogen group.
  • the dinonanol malonate represented by the above formula (4) is particularly preferably dimethyl malonate.
  • R 6 and R 7 in the above formula (5) each represent a hydrogen atom, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted aryl group, a substituted group or An aryl fluorenyl group having no substituent. Further, a ring having 3 to 7 carbon atoms may be formed from R 6 and R 7 .
  • a linear or branched mercapto group having 1 to 8 carbon atoms is preferable.
  • aryl group a phenyl group, a tolyl group, a xylyl group or a naphthyl group is preferable.
  • aryl group a benzyl group or a phenethyl group is preferable.
  • substituent of the group and the aryl group include an alcohol, an amine, a carboxylic acid, an ester, an amide, an ether, an acyl group, a halogen group and the like.
  • the amine compound represented by the above formula (5) is particularly preferably benzylamine.
  • nucleophiles are added in an amount of 1 to 4 moles, preferably 2 to 3 moles, per mole of the olefin.
  • N,S-bis(trimethylsilyl)acetamide may be used in combination.
  • the inorganic base sodium carbonate, potassium carbonate, sodium acetate, potassium acetate or the like can be used, and among them, sodium acetate is particularly preferable.
  • the N,S-bis(trimethylsilyl) acetamide (BSA) is added in an amount of 0.8 to 1.5, preferably 0.9 to 1.1, based on the molar ratio of the olefin. Further, the amount of the inorganic base added is sufficient as the amount of the catalyst.
  • the reaction of the present invention is usually carried out in the presence of a solvent.
  • the solvent to be used is not particularly limited as long as it is a solvent capable of dissolving the raw material and has no activity on the product, and examples thereof include dichloromethane, acetonitrile, tetrahydrofuran, and 1,2-dichloroethane. ⁇ , ⁇ '-dimethylformamide, diethyl ether or toluene.
  • the Pd catalyst used in the present invention is a Pd transition metal complex compound having a bisphosphine compound represented by the above formula (1) or (2) as a ligand.
  • Pd transition metal complex compound examples include the following ligands.
  • L in the above represents a bisphosphine ligand represented by the above formula (1) or (2).
  • a compound having a main stereo configuration of an S type can be obtained by using a Pd transition metal catalyst having a bisphosphine compound of the above formula (1) as a ligand; (2)
  • the bisphosphine compound is a ligand Pd transition metal
  • the catalyst can be obtained as a compound having a predominantly stereo configuration.
  • the chiral ligands (0.015 mmol) and [PdO/ 3 -C 3 3 ⁇ 4 )Cl] 2 (2.3 mg, 0.0063 mmol) shown in Table 2 and Table 3 were dissolved in Table 2 and Table 3 under a nitrogen atmosphere.
  • the in-situ catalyst was prepared by stirring at room temperature for 1 hour in a dry solvent of the kind shown (1 mL). A solution of 1,3-diphenylallyl acetate (126 mg, 0.5 mmol) and dried dry solvent (1 mL) of the type shown in Table 2 was added thereto. After 10 minutes, benzylamine (131 L, 1.5 mmol) was added, and the reaction was monitored by TLC, and the reaction was completed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de stéréosélectivité dans une réaction de substitution allylique par catalyse au palladium. Un catalyseur à base de palladium est appliqué à la réaction de substitution asymétrique allylique, dans laquelle l'alcène contenant le groupe partant dans la position du substituant allylique réagit avec le nucléophile pour obtenir la substitution allylique stéréosélective. Le ligand dans le catalyseur à base de palladium est le ligand diphosphine à base de métallocène de formule (1) ou (2), dans lesquelles : R1 est un alkyle C1-C4 ou les groupes contenant un substituant amide ; R2 est hydrogène ou alkyle C1-C4 ou acétyle ; et M est un atome de fer ou un atome de ruthénium.
PCT/CN2008/072561 2007-09-27 2008-09-27 Procédé de stéréosélectivité dans une réaction de substitution allylique par catalyse au palladium WO2009043303A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200880108610A CN101808975A (zh) 2007-09-27 2008-09-27 由Pd-催化的烯丙基取代反应的立体选择性制造方法

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CN200710046457.6 2007-09-27
CNA2007100464576A CN101143818A (zh) 2007-09-27 2007-09-27 Pd-催化的烯丙基取代反应中的对映选择性反转的方法

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Publication number Priority date Publication date Assignee Title
CN102452911B (zh) * 2010-10-22 2014-08-27 上海交通大学 基于钯催化的烯丙基取代反应实现c-n键转变c-c键的方法
CN104447495B (zh) * 2013-09-17 2017-08-01 上海交通大学 手性β‑取代‑α,β‑不饱和氨基醇类化合物的制备方法
CN107074675B (zh) * 2015-01-30 2019-12-20 四川海思科制药有限公司 一种手性的2-[1-环丙基乙基]-6-异丙基-苯酚的制备方法
CN113980053B (zh) * 2021-11-08 2023-11-03 百色学院 手性硫醚-膦化合物及其制备方法
CN115057885B (zh) * 2022-06-23 2023-10-17 上海交通大学 一种苯乙烯轴手性膦配体及其合成方法与应用

Citations (2)

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CN1876668A (zh) * 2006-06-08 2006-12-13 上海交通大学 C2－对称的只具有面手性的二茂钌双膦配体
CN1876667A (zh) * 2006-06-08 2006-12-13 上海交通大学 C2－对称的只具有面手性的二茂钌双膦配体的合成方法

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CN1876668A (zh) * 2006-06-08 2006-12-13 上海交通大学 C2－对称的只具有面手性的二茂钌双膦配体
CN1876667A (zh) * 2006-06-08 2006-12-13 上海交通大学 C2－对称的只具有面手性的二茂钌双膦配体的合成方法

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Title
LIU, DELONG ET AL.: "Novel C2-symmetric planar chiral diphosphine ligands and their application in Pd-catalyzed asymmetric allylic substitutions", JOURNAL OF ORGANIC CHEMISTRY, vol. 72, no. 18, April 2007 (2007-04-01), pages 6992 - 6997 *
LIU, DELONG ET AL.: "Palladium-catalyzed asymmetric allylic alkylation with an enamine as the nucleophilic reagent", TETRAHEDRON LETTERS, vol. 48, no. 43, 4 September 2007 (2007-09-04), pages 7591 - 7594 *
XIE, FANG ET AL.: "Reversal in enantioselectivity for the palladium-catalyzed asymmetric allylic substitution with novel metallocene-based planar chiral diphosphine ligands", TETRAHEDRON LETTERS, vol. 49, no. 6, January 2008 (2008-01-01), pages 1012 - 1015 *
ZHANG, WANBIN ET AL.: "C2-Symmetric Diphosphine Ligands with Only the Planar Chirality of Ferrocene for the Palladium-Catalyzed Asymmetric Allylic Alkylation", JOURNAL OF ORGANIC CHEMISTRY, vol. 64, no. 17, 1999, pages 6247 - 6251 *

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CN101808975A (zh) 2010-08-18
CN101143818A (zh) 2008-03-19

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