Method for producing optically active compound, and novel metal-diamine complex

Patent metadata

Field	Value
Publication number	US-2016347678-A1
Application number	US-201515117333-A
Country	US
Kind code	A1
Filing date	Feb 13, 2015
Priority date	Feb 14, 2014
Publication date	Dec 1, 2016
Grant date	—

Abstract

The present invention pertains to a method for producing an optically active compound which includes a step for reducing an imino group of an imine compound or a step for reducing an unsaturated bond of a heterocyclic compound, while in the presence of hydrogen gas as a hydrogen donor and one or more types of complexes selected from a group consisting of a complex represented by general formula (1), a complex represented by general formula (2), a complex represented by general formula (3), and a complex represented by general formula (4) (the general formulas (1)-(4) are as stipulated by claim 1 ).

First claim

1 . A method for producing an optically active compound, comprising the step of:
reducing an imino group of an imine compound or reducing an unsaturated bond of a heterocyclic compound in the presence of at least one complex selected from complexes represented by general formula (1) below, complexes represented by general formula (2) below, complexes represented by general formula (3) below, and complexes represented by general formula (4) below and of hydrogen gas serving as a hydrogen donor:

wherein
* indicates an asymmetric carbon atom,
R 1 represents a group selected from alkyl groups having 1 to 10 carbon atoms, halogenated alkyl groups having 1 to 10 carbon atoms, and aryl groups having 6 to 30 carbon atoms, wherein said aryl groups may have one or more substituents selected from alkyl groups having 1 to 10 carbon atoms, halogenated alkyl groups having 1 to 10 carbon atoms, and halogen atoms,
R 2 and R 3 each independently represent a group selected from alkyl groups having 1 to 10 carbon atoms, phenyl groups, and cycloalkyl groups having 3 to 8 carbon atoms, wherein said phenyl groups may have one or more substituents selected from alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and halogen atoms, and wherein said cycloalkyl groups may have one or more substituents selected from alkyl groups having 1 to 10 carbon atoms, or R 2 and R 3 form a ring together with the carbon atoms to which R 2 and R 3 are bonded,
Y represents a hydrogen atom or a deuterium atom,
R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 each independently represent a group selected from a hydrogen atom, alkyl groups having 1 to 10 carbon atoms, silyl groups having 1 to 3 alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and —C(═O)—OR 22 , wherein R 22 represents an alkyl group having 1 to 10 carbon atoms, a heteroaryl group having 4 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and
Q − represents a counter anion;

wherein
* indicates an asymmetric carbon atom,
R 1 , R 2 , R 3 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , and Y are as defined above,
A represents a group selected from a trifluoromethanesulfonyloxy group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, a benzenesulfonyloxy group, a hydrogen atom, a deuterium atom, and halogen atoms, and
j and k each represent 0 or 1, provided that j+k is not 1;

wherein
* indicates an asymmetric carbon atom,
R 1 , R 2 , R 3 , A, and Y are as defined above,
M represents iridium or rhodium,
L represents a cyclopentadienyl or pentamethylcyclopentadienyl ligand, and
j and k each represent 0 or 1, provided that j+k is not 1; and

wherein
* indicates an asymmetric carbon atom, and
R 1 , R 2 , R 3 , Y, M, L, and Q − are as defined above.

2 . A ruthenium complex represented by general formula (1):

wherein
* indicates an asymmetric carbon atom,
R 1 represents a group selected from alkyl groups having 1 to 10 carbon atoms, halogenated alkyl groups having 1 to 10 carbon atoms, and aryl groups having 6 to 30 carbon atoms, wherein said aryl groups may have one or more substituents selected from alkyl groups having 1 to 10 carbon atoms, halogenated alkyl groups having 1 to 10 carbon atoms, and halogen atoms,
R 2 and R 3 each independently represent a group selected from alkyl groups having 1 to 10 carbon atoms, phenyl groups, and cycloalkyl groups having 3 to 8 carbon atoms, wherein said phenyl groups may have one or more substituents selected from alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and halogen atoms, and wherein said cycloalkyl groups may have one or more substituents selected from alkyl groups having 1 to 10 carbon atoms, or R 2 and R 3 form a ring together with the carbon atoms to which R 2 and R 3 are bonded,
Y represents a hydrogen atom or a deuterium atom,
R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 each independently represent a group selected from a hydrogen atom, alkyl groups having 1 to 10 carbon atoms, silyl groups having 1 to 3 alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and —C(═O)—OR 22 , wherein R 22 represents an alkyl group having 1 to 10 carbon atoms, a heteroaryl group having 4 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and
Q − represents a counter anion.

3 . An iridium or rhodium complex represented by general formula (4):

wherein
* indicates an asymmetric carbon atom,
R 1 represents a group selected from alkyl groups having 1 to 10 carbon atoms, halogenated alkyl groups having 1 to 10 carbon atoms, and aryl groups having 6 to 30 carbon atoms, wherein said aryl groups may have one or more substituents selected from alkyl groups having 1 to 10 carbon atoms, halogenated alkyl groups having 1 to 10 carbon atoms, and halogen atoms,
R 2 and R 3 each independently represent a group selected from alkyl groups having 1 to 10 carbon atoms, phenyl groups, and cycloalkyl groups having 3 to 8 carbon atoms, wherein said phenyl groups may have one or more substituents selected from alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and halogen atoms, and wherein said cycloalkyl groups may have one or more substituents selected from alkyl groups having 1 to 10 carbon atoms, or R 2 and R 3 form a ring together with the carbon atoms to which R 2 and R 3 are bonded,
Y represents a hydrogen atom or a deuterium atom,
M represents iridium or rhodium,
L represents a cyclopentadienyl or pentamethylcyclopentadienyl ligand, and
Q − represents a counter anion.

4 . An asymmetric reduction catalyst comprising the complex according to claim 2 .

5 . An asymmetric reduction catalyst comprising the complex according to claim 3 .

Assignees

• Takasago Perfumery Co Ltd

Inventors

• Touge Taichiro
• Nara Hideki

Classifications

• C07B53/00 Primary

  Asymmetric syntheses · CPC title

• C07F15/0046

  Ruthenium compounds · CPC title

• C07D209/08

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring · CPC title

• C07D209/94

  containing carbocyclic rings other than six-membered · CPC title

• C07D265/36

  condensed with one six-membered ring · CPC title