Ruthenium complex and method for preparing optically active alcohol compounds using the same as a catalyst

Patent metadata

Field	Value
Publication number	US-9255049-B2
Application number	US-201214009687-A
Country	US
Kind code	B2
Filing date	Apr 2, 2012
Priority date	Apr 6, 2011
Publication date	Feb 9, 2016
Grant date	Feb 9, 2016

Abstract

The present invention provides a novel ruthenium complex which has an excellent catalytic activity in terms of reactivity for an asymmetric reduction of a carbonyl compound and enantioselectivity, a catalyst using the ruthenium complex, and a method for preparing optically active alcohol compounds using the ruthenium complex. The present invention relates to a ruthenium complex having a ruthenacycle structure, a catalyst for an asymmetric reduction consisting of the ruthenium complex, and a method for preparing optically active alcohol compounds using the ruthenium complex.

First claim

The invention claimed is:

1. A ruthenium complex having the following Formula (2)

(wherein, P∩P represents a diphosphine; Y − represents a counter anion; R a , R b , and R c each independently represent a hydrogen atom, an optionally substituted C 1 -C 20 alkyl group, an optionally substituted C 2 -C 20 alkenyl group, an optionally substituted C 3 -C 8 cycloalkyl group, an optionally substituted C 7 -C 20 aralkyl group, an optionally substituted aryl group or an optionally substituted heterocyclic group, and R b and R c may form an alkylene group or an alkylenedioxy group; R d , R e , R f and R g each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogen atom, an optionally substituted aryl group, an optionally substituted C 3 -C 8 cycloalkyl group, a tri-substituted silyl group or an alkoxy group having 1 to 20 carbon atoms; R N1 , R N2 , R N3 and R N4 each independently represent a hydrogen atom, an optionally substituted C 1 -C 20 alkyl group, an optionally substituted C 2 -C 20 alkenyl group, an optionally substituted C 7 -C 20 aralkyl group or an optionally substituted C 3 -C 8 cycloalkyl group, and at least one of R N1 , R N2 , R N3 and R N4 represents a hydrogen atom; and R N1 and R a may form an alkylene group).

2. The ruthenium complex according to claim 1 , wherein the ruthenium complex is having the following Formula (3)

(wherein, P∩P represents a diphosphine; Y − represents a counter anion; R a and R b each independently represent a hydrogen atom, an optionally substituted C 1 -C 20 alkyl group, an optionally substituted C 2 -C 20 alkenyl group, an optionally substituted C 3 -C 8 cycloalkyl group, an optionally substituted C 7 -C 20 aralkyl group, an optionally substituted aryl group or an optionally substituted heterocyclic group; R N1 , R N2 , R N3 and R N4 each independently represent a hydrogen atom, an optionally substituted C 1 -C 20 alkyl group, an optionally substituted C 2 -C 20 alkenyl group, an optionally substituted C 7 -C 20 aralkyl group or an optionally substituted C 3 -C 8 cycloalkyl group, and at least one of R N1 , R N2 , R N3 and R N4 represents a hydrogen atom; and R N1 and R a may form an alkylene group).

3. The ruthenium complex according to claim 1 , wherein the diphosphine indicated as P∩P is a diphosphine having the following Formula (4)
R 1 R 2 P-Q-PR 3 R 4   (4)

(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 R 1 and R 2 and/or R 3 and R 4 may form a ring; and Q represents an optionally substituted divalent arylene group, a biphenyldiyl group, a binaphthalenediyl group, a bipyridinediyl group, a paracyclophanediyl group or a ferrocenediyl group).

4. The ruthenium complex according to claim 1 , wherein the diphosphine indicated as P∩P is an optically active diphosphine.

5. The ruthenium complex according to claim 4 , wherein the optically active diphosphine indicated as P∩P is a diphosphine having the following Formula (5)

(wherein, R 1′ , R 2′ , R 3′ and R 4′ each independently represent a phenyl group, a cyclopentyl group or a cyclohexyl group, and any of which is optionally substituted with a substituent group selected from a group consisting of an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms; R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a halogenated alkyl group or an dialkylamino group having 1 to 4 carbon atoms, and two of R 5 , R 6 and R 7 may 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 form an optionally substituted alkylene group; an optionally substituted alkylenedioxy group; or an optionally substituted aromatic ring; and R 7 and R 8 may form an optionally substituted alkylene group; an optionally substituted alkylenedioxy group; or an optionally substituted aromatic ring, with the proviso that any of R 7 and R 8 is not a hydrogen atom).

6. The ruthenium complex according to claim 5 , wherein R 1′ , R 2′ , R 3′ and R 4′ in the Formula (5) is a 3,5-xylyl group.

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

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

9. An asymmetric reduction catalyst comprising the ruthenium complex according to claim 6 .

10. The ruthenium complex according to claim 2 , wherein the diphosphine indicated as P∩P is a diphosphine having the following Formula(4)
R 1 R 2 P-Q-PR 3 R 4   (4)

(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 R 1 and R 2 and/or R 3 and R 4 may form a ring; and Q represents an optionally substituted divalent arylene group, a biphenyldiyl group, a binaphthalenediyl group, a bipyridinediyl group, a paracyclophanediyl group or a ferrocenediyl group).

11. The ruthenium complex according to claim 10 , wherein the diphosphine indicated as P∩P is an optically active diphosphine.

12. The ruthenium complex according to claim 11 , wherein the optically active diphosphine indicated as P∩P is a diphosphine having the following Formula (5)

(wherein, R 1′ , R 2′ , R 3′ and R 4′ each independently represent a phenyl group, a cyclopentyl group or a cyclohexyl group, and any of which is optionally substituted with a substituent group selected from a group consisting of an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms; R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a halogenated alkyl group or an dialkylamino group having 1 to 4 carbon atoms, and two of R 5 , R 6 and R 7 may 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 form an optionally substituted alkylene group; an optionally substituted alkylenedioxy group; or an optionally substituted aromatic ring; and R 7 and R 8 may form an optionally substituted alkylene group; an optionally substituted alkylenedioxy group; or an optionally substituted aromatic ring, with the proviso that any of R 7 and R 8 is not a hydrogen atom).

13. The ruthenium complex according to claim 12 , wherein R 1′ , R 2′ , R 3′ and R 4′ in the Formula (5) is a 3,5-xylyl group.

14. An asymmetric reduction catalyst comprising the ruthenium complex according to claim 11 .

15. An asymmetric reduction catalyst comprising the ruthenium complex according to claim 12 .

16. An asymmetric reduction catalyst comprising the ruthenium complex ac

Assignees

• Hori Kiyoto
• Matsumura Kazuhiko
• Takasago Perfumery Co Ltd

Inventors

• Hori Kiyoto
• Matsumura Kazuhiko

Classifications

• C07F9/65517

  condensed with carbocyclic rings or carbocyclic ring systems · CPC title

• C07F9/5027

  Polyphosphines · CPC title

• B01J2531/821

  Ruthenium · CPC title

• B01J31/1805

  the ligands containing nitrogen · CPC title

• C07B2200/07

  Optical isomers · CPC title