Process for producing optically active amine

Patent metadata

Field	Value
Publication number	US-9328079-B2
Application number	US-201314421481-A
Country	US
Kind code	B2
Filing date	Sep 6, 2013
Priority date	Sep 7, 2012
Publication date	May 3, 2016
Grant date	May 3, 2016

Abstract

A process for producing an optically active amine compound, characterized by asymmetrically hydrogenating a prochiral carbon-nitrogen double bond in the presence of a ruthenium complex represented by general formula (1) or (2) (wherein P represents an optically active diphosphine, X represents an anionic group, and Ar represents an optionally substituted arylene group).

First claim

The invention claimed is:

1. A method for producing an optically active amine compound, comprising:
performing an asymmetric hydrogenation of a prochiral carbon-nitrogen double bond in the presence of a ruthenium complex of the following general formula (1) or (2):

wherein

represents an optically active diphosphine; X represents an anionic group; R a , R b , and R c each independently represent a hydrogen atom, an optionally substituted C 1 to C 20 alkyl group, an optionally substituted C 2 to C 20 alkenyl group, an optionally substituted C 3 to C 8 cycloalkyl group, an optionally substituted C 7 to C 20 aralkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group, or R b and R c may together form an optionally substituted alkylene group or an optionally substituted alkylenedioxy group; R N1 , R N2 , R N3 , and R N4 each independently represent a hydrogen atom, an optionally substituted C 1 to C 20 alkyl group, an optionally substituted C 2 to C 20 alkenyl group, an optionally substituted C 7 to C 20 aralkyl group, or an optionally substituted C 3 to C 8 cycloalkyl group, provided that at least one of R N1 , R N2 , R N3 , and R N4 is a hydrogen atom; R N1 and R a may together form an optionally substituted alkylene group; n represents an integer of 0 to 3; and Ar represents an optionally substituted arylene group.

2. The production method according to claim 1 , wherein
the ruthenium complex is of the following general formula (3) or (4):

wherein

represents an optically active diphosphine; X represents an anionic group; R a , R b , and R c each independently represent a hydrogen atom, an optionally substituted C 1 to C 20 alkyl group, an optionally substituted C 2 to C 20 alkenyl group, an optionally substituted C 3 to C 8 cycloalkyl group, an optionally substituted C 7 to C 20 aralkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group, or R b and R c may together form an optionally substituted alkylene group or an optionally substituted alkylenedioxy group; R d , R e , R f , and R g each independently represent a hydrogen atom, an optionally substituted C 1 to C 20 alkyl group, a C 1 to C 5 halogenated alkyl group, a halogen atom, an optionally substituted aryl group, an optionally substituted C 3 to C 8 cycloalkyl group, a tri-substituted silyl group, or an optionally substituted C 1 to C 20 alkoxy group; R N1 , R N2 , R N3 , and R N4 each independently represent a hydrogen atom, an optionally substituted C 1 to C 20 alkyl group, an optionally substituted C 2 to C 20 alkenyl group, an optionally substituted C 7 to C 20 aralkyl group, or an optionally substituted C 3 to C 8 cycloalkyl group, provided that at least one of R N1 , R N2 , R N3 , and R N4 is a hydrogen atom; and R N1 and R a may together form an optionally substituted alkylene group.

3. The production method according to claim 1 , wherein
the optically active diphosphine represented by

is a diphosphine of the following general formula (5):
R 1 R 2 P-Q-PR 3 R 4   (5),

wherein R 1 , R 2 , R 3 , and R 4 each independently represent an optionally substituted aryl group, an optionally substituted cycloalkyl group, or an optionally substituted alkyl group, and the pair of R 1 and R 2 and/or the pair of R 3 and R 4 may together form a ring; and Q represents biphenyldiyl, binaphthalenediyl, bipyridinediyl, paracyclophanediyl, or ferrocenediyl group, has an asymmetric structure, and may be substituted.

4. The production method according to claim 2 , wherein
the optically active diphosphine represented by

is a diphosphine of the following general formula (5):
R 1 R 2 P-Q-PR 3 R 4   (5),

wherein R 1 , R 2 , R 3 , and R 4 each independently represent an optionally substituted aryl group, an optionally substituted cycloalkyl group, or an optionally substituted alkyl group, and the pair of R 1 and R 2 and/or the pair of R 3 and R 4 may together form a ring; and Q represents biphenyldiyl, binaphthalenediyl, bipyridinediyl, paracyclophanediyl, or ferrocenediyl group, has an asymmetric structure, and may be substituted.

5. The production method according to claim 3 , wherein
the

is an optically active diphosphine of the following general formula (6):

wherein R 1′ , R 2′ , R 3′ , and R 4′ each independently represent a phenyl group optionally substituted by a substituent(s) selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and alkoxy groups having 1 to 4 carbon atoms; a cyclopentyl group; or a cyclohexyl group; R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted alkoxy group having 1 to 4 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, or a dialkylamino group, or two of R 5 , R 6 , and R 7 may together form an optionally substituted alkylene group; an optionally substituted alkylenedioxy group; or an optionally substituted aromatic ring, two of R 8 , R 9 , and R 10 may together form an optionally substituted alkylene group; an optionally substituted alkylenedioxy group; or an optionally substituted aromatic ring, R 7 and R 8 may together form an optionally substituted alkylene group; an optionally substituted alkylenedioxy group; or an optionally substituted aromatic ring, provided that neither R 7 nor R 8 is a hydrogen atom; and * indicates axial chirality.

6. The production method according to claim 4 , wherein
the

is an optically active diphosphine of the following general formula (6):

wherein R 1′ , R 2′ , R 3′ , and R 4′ each independently represent a phenyl group optionally substituted by a substituent(s) selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and alkoxy groups having 1 to 4 carbon atoms; a cyclopentyl group; or a cyclohexyl group; R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted alkoxy group having 1 to 4 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, or a dialkylamino group, or two of R 5 , R 6 , and R 7 may together form an optionally substituted alkylene group; an optionally substituted alkylenedioxy group; or an optionally substituted aromatic ring, two of R 8 , R 9 , and R 10 may together form an optionally substituted alkylene group; an optionally substituted alkylenedioxy group; or an optionally substituted aromatic ring, R 7 and R 8 may together form an optionally substituted alkylene group; an opt

Assignees

• Takasago Perfumery Co Ltd

Inventors

• Ohkuma Takeshi
• Arai Noriyoshi
• Matsumura Kazuhiko

Classifications

• C07D265/36

  condensed with one six-membered ring · CPC title

• C07D279/16 Primary

  condensed with one six-membered ring · CPC title

• C07D241/42

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

• C07B53/00

  Asymmetric syntheses · CPC title