JP4853757B2 - Optically active sulfur-bridged dinuclear ruthenium complex, method for producing the same, method for producing optically active compound using such a catalyst, and novel optically active compound - Google Patents

Description

  The present invention relates to an optically active ruthenium complex useful as a catalyst for asymmetric synthesis, a method for producing the same, and a method for producing an optically active compound using the same as a catalyst.

  The optically active compound obtained by using the optically active ruthenium complex of the present invention for the reaction is useful as a pharmaceutical / pesticidal intermediate and a raw material for electronic materials.

  Conventionally, optically active ruthenium complexes represented by the following general formula (9) or general formula (10) and asymmetric synthesis reactions using them as catalysts are known.

[In General Formula (9) or General Formula (10), R ₁ S represents a group represented by the following General Formula (11) or General Formula (12), and Cp ^* is η ⁵ -C ₅ Me _5. (Pentamethylcyclopentadiene).

(In the above general formula (11) or general formula (12), R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ represents a phenyl group, a 1-naphthyl group, a 2-naphthyl group, A cycloalkyl group having 3 to 8 carbon atoms, a phenyl group having 1 to 5 carbon atoms substituted with a linear or branched alkyl group having 1 to 5 carbon atoms, and a linear or branched alkyloxy group having 1 to 5 carbon atoms In which the nucleus is substituted with 1 to 5 nuclei, the phenyl group is substituted with 1 to 5 nuclei with halogen, and the 1 to naphthyl is substituted with 1 to 5 carbon atoms with a linear or branched alkyl group having 1 to 5 carbon atoms 1-naphthyl group in which the nucleus is 1 to 5 substituted with a linear or branched alkyloxy group having 1 to 5 carbon atoms, 1-naphthyl group in which the nucleus is substituted with 1 to 5 carbon atoms, 1 to 5 carbon atoms A linear or branched alkyl group with 1-5 nuclei A 2-naphthyl group having 1 to 5 carbon atoms substituted with a straight chain or branched alkyloxy group having 1 to 5 carbon atoms, or a 2-naphthyl group having 1 to 5 carbon atoms substituted with halogen. Shown)]]
Further, using the catalyst represented by the general formula (9) or the general formula (10), the following general formula (6)

(In the formula, R ₄ is a linear or branched alkyl group having 1 to 10 carbon atoms, phenyl group, 1-naphthyl group, 2-naphthyl group, cycloalkyl group having 3 to 8 carbon atoms, or 1 to 5 carbon atoms. A phenyl group in which the nucleus is substituted by 1 to 5 with a linear or branched alkyl group, a phenyl group in which the nucleus is substituted with a linear or branched alkyloxy group having 1 to 5 carbon atoms, and a nucleus with halogen. 1- to 5-substituted phenyl group, 1- to 5-carbon linear or branched alkyl group, 1-naphthyl group whose nucleus is substituted to 1-5, linear or branched alkyloxy group having 1 to 5 carbon atoms 1-naphthyl group in which the nucleus is substituted with 1 to 5 in the nucleus, 1-naphthyl group in which the nucleus is substituted with 1 to 5 in the halogen, or a linear or branched alkyl group having 1 to 5 carbon atoms is substituted with 1 to 5 in the nucleus 2-naphthyl group, straight chain having 1 to 5 carbon atoms Represents a 2-naphthyl group in which the nucleus is substituted by 1 to 5 with a branched alkyloxy group or a 2-naphthyl group in which the nucleus is substituted with 1 to 5 by halogen.
And propargyl alcohol represented by the following general formula (7)

(Wherein R ₅ and R ₆ are each independently hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkynyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. A linear or branched alkenyl group, a phenyl group, a benzyl group, a 1-naphthyl group, a 2-naphthyl group, a phenyl group in which a nucleus is substituted with a linear or branched alkyl group having 1 to 5 carbon atoms, A phenyl group in which the nucleus is substituted by 1 to 5 carbon atoms with a linear or branched alkoxy group having 1 to 5 carbon atoms, a phenyl group in which the nucleus is substituted by 1 to 5 carbon atoms with a halogen atom, a linear or branched chain having 1 to 5 carbon atoms 1-naphthyl group having 1-5 substituted nucleus with alkyl group, 1-naphthyl group having 1-5 substituted nucleus with straight chain or branched alkoxy group having 1-5 carbon atoms, 1-naphthyl group having 1 atom substituted with halogen atom A 5-substituted 1-naphthyl group, A 2-naphthyl group in which the nucleus is substituted with 1 to 5 linear or branched alkyl groups having 1 to 5 prime atoms, or a 2- to 1-substituted nucleus with linear or branched alkoxy groups having 1 to 5 carbon atoms. A naphthyl group or a 2-naphthyl group in which the nucleus is substituted by 1 to 5 with a halogen atom.)
Is reacted with a ketone represented by the following general formula (8):

(In the above formula, R ₄ , R ₅ and R ₆ have the same definition as above, and * represents an asymmetric carbon.)
A method for obtaining a ketone derivative represented by the formula (1) is known (for example, see Patent Document 1).
JP 2002-265435 A

However, the optical activity represented by the above general formula (9) or general formula (10), which may have a substituted phenyl group (but does not include an aromatic substituent such as a phenyl ring) as the substituent R ₃ . The reaction of using the ruthenium complex as a catalyst to obtain the acetone represented by the general formula (8) by the reaction of the propargyl alcohol represented by the general formula (6) and the ketone represented by the general formula (7) is as follows: Although optical selectivity was exhibited, the optical selectivity remained as low as 28% ee at the maximum, and it could not be a practical method.

  As a result of intensive studies on the development of a novel optically active catalyst and an asymmetric synthesis reaction using the same, the present inventors have found that the following general formula (1)

[R ₁ S in the above formula represents a group represented by the following general formula (2), and Cp ^* represents η ⁵ -C ₅ Me ₅ (pentamethylcyclopentadiene).

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
And an optically active catalyst comprising an optically active ruthenium complex having a phenyl ring substituted with an aromatic substituent such as a phenyl ring as the substituent R _3. It has been found that induction is possible, and the present invention has been completed.

  That is, the present invention provides an optically active sulfur-bridged dinuclear ruthenium complex, a method for producing the same, a method for producing an optically active compound using such a catalyst, and a novel optically active compound as described below.

  1. General formula (1)

[R ₁ S in the above formula represents the general formula (2)

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
And Cp ^* represents η ⁵ -C ₅ Me ₅ (pentamethylcyclopentadiene). ]
An optically active ruthenium complex represented by:

2. In the general formula (1), R ₂ is an ethyl group, R ₃ is a 2-methoxy-5 - phenylphenyl group, 2-methoxy-5- (2-naphthyl) phenyl group, 2- (2-propoxy) -5- Phenylphenyl group, 2,5-diphenylphenyl group, 2,3,5-triphenylphenyl group, 2,3,5- (4-methylphenyl) phenyl group or 2,3,5- (4-tert-butyl) The optically active ruthenium complex represented by the general formula (1) according to claim 1, which is a phenyl) phenyl group.

  3. General formula (3)

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
An optically active disulfide compound represented by:

4). In the general formula (3), R ₂ is an ethyl group, R ₃ is a 2-methoxy-5-phenyl group, 2-methoxy-5- (2-naphthyl) phenyl group, 2- (2-propoxy) -5- Phenyl group, 2,5-diphenylphenyl group, 2,3,5-triphenylphenyl group, 2,3,5- (4-methylphenyl) phenyl group or 2,3,5- (4-tert-butylphenyl) 2.) a phenyl group; An optically active disulfide compound represented by the general formula (3) described in 1.

5). Ruthenium complex (Cp ^* RuCl) ₄ [where Cp ^* represents η ⁵ -C ₅ Me ₅ (pentamethylcyclopentadiene). ] And general formula (3)

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.), Which is reacted with a disulfide compound represented by the general formula (1)

[R ₁ S in the above formula represents the general formula (2)

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
And Cp ^* represents η ⁵ -C ₅ Me ₅ (pentamethylcyclopentadiene). ]
The manufacturing method of the optically active ruthenium complex shown by these.

  6). General formula (4)

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
An optically active alcohol represented by

7). In the above general formula (4), R ₂ is an ethyl group, R ₃ is a 2-methoxy-5-phenyl group, 2-methoxy-5- (2-naphthyl) phenyl group, 2- (2-propoxy) -5- Phenyl group, 2,5-diphenylphenyl group, 2,3,5-triphenylphenyl group, 2,3,5- (4-methylphenyl) phenyl group or 2,3,5- (4-tert-butylphenyl) 5.) A phenyl group. An optically active alcohol represented by the general formula (4) described in 1.

  8). General formula (4)

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
An optically active alcohol represented by the general formula (3) is substituted with an acetylthio group by a steric inversion reaction, then reduced, and then dimerized by oxidation.

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
The manufacturing method of optically active disulfides shown by these.

  9. General formula (5)

(In the above formula, R ₃ is a phenyl group in which the nucleus is substituted with 1 to 5 nuclei, a phenyl group in which the nucleus is substituted with 1 to 5 in the substituted phenyl group, or a phenyl group in which the nucleus is substituted with 1 to 5 in the naphthyl group A phenyl group in which the nucleus is substituted by 1 to 5 with a substituted naphthyl group, a 2-alkoxyphenyl group in which the nucleus is substituted by 1 to 4 by a phenyl group, or a 2-alkoxyphenyl group in which the nucleus is substituted by 1 to 4 by a substituted phenyl group And a 2-alkoxyphenyl group in which the nucleus is substituted by 1 to 4 with a naphthyl group or a 2-alkoxyphenyl group in which the nucleus is substituted by 1 to 4 with a substituted naphthyl group
Wherein the aldehydes represented by formula (4) are asymmetrically alkylated

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
The manufacturing method of optically active alcohol shown by these.

  10. Above 1. Or 2. A catalyst for asymmetric synthesis reaction comprising the optically active ruthenium complex described in 1.

  11. 10. above. In the presence of the catalyst for asymmetric synthesis reaction described in formula (6)

(In the above formula, R ₄ is a linear or branched alkyl group having 1 to 10 carbon atoms, phenyl group, 1-naphthyl group, 2-naphthyl group, cycloalkyl group having 3 to 8 carbon atoms, A phenyl group in which the nucleus is substituted with 1 to 5 linear or branched alkyl groups, a phenyl group in which the nucleus is substituted with 1 to 5 linear or branched alkyloxy groups, and a nucleus with halogen 1 to 5 substituted phenyl groups, phenyl groups each substituted 1 to 5 with phenyl groups, 1 to 5 carbon atoms linear or branched alkyl groups with 1 to 5 nucleus substituted 1-naphthyl groups 1-naphthyl group having 1 to 5 carbon atoms substituted with a linear or branched alkyloxy group having 1 to 5 carbon atoms, 1-naphthyl group having 1 to 5 carbon atoms substituted with halogen, 1 to 5 carbon atoms Linear or branched alkyl group with a nucleus of 1 5-substituted 2-naphthyl group, 2-naphthyl group having 1 to 5 carbon atoms substituted with a linear or branched alkyloxy group having 1 to 5 carbon atoms, or 2-naphthyl having 1 to 5 nucleus atoms substituted with halogen Group.)
And propargyl alcohol represented by the general formula (7)

(Wherein R ₅ and R ₆ are each independently hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkynyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. A linear or branched alkenyl group, a phenyl group, a benzyl group, a 1-naphthyl group, a 2-naphthyl group, a phenyl group in which a nucleus is substituted with a linear or branched alkyl group having 1 to 5 carbon atoms, A phenyl group in which the nucleus is substituted by 1 to 5 carbon atoms with a linear or branched alkoxy group having 1 to 5 carbon atoms, a phenyl group in which the nucleus is substituted by 1 to 5 carbon atoms with a halogen atom, a linear or branched chain having 1 to 5 carbon atoms 1-naphthyl group having 1-5 substituted nucleus with alkyl group, 1-naphthyl group having 1-5 substituted nucleus with straight chain or branched alkoxy group having 1-5 carbon atoms, 1-naphthyl group having 1 atom substituted with halogen atom A 5-substituted 1-naphthyl group, A 2-naphthyl group in which the nucleus is substituted with 1 to 5 linear or branched alkyl groups having 1 to 5 prime atoms, or a 2- to 1-substituted nucleus with linear or branched alkoxy groups having 1 to 5 carbon atoms. A naphthyl group or a 2-naphthyl group in which the nucleus is substituted by 1 to 5 with a halogen atom.)
Wherein the ketone represented by the general formula (8) is reacted

(Wherein R ₄ , R ₅ and R ₆ have the same definition as above, and * represents an asymmetric carbon.)
The manufacturing method of the ketone derivative shown by these.

  According to the present invention, a novel optically active ruthenium complex and a method for producing the same are provided. In addition, the optically active ruthenium complex of the present invention is a novel catalyst for asymmetric synthesis reaction, and the optically active compound synthesized using the same is useful as a raw material for pharmaceutical / pesticidal intermediates and electronic materials. The invention is very significant industrially.

  The optically active ruthenium complex of the present invention is a compound represented by the following general formula (1).

[R ₁ S in the above formula represents a group represented by the following general formula (2), and Cp ^* represents η ⁵ -C ₅ Me ₅ (pentamethylcyclopentadiene).

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
In the present invention, as the group represented by the general formula (2), specifically, (1R) -1- (2-phenylphenyl) ethyl-1-thio group, (1R) -1- (3- Phenylphenyl) ethyl-1-thio group, (1R) -1- (4-phenylphenyl) ethyl-1-thio group, (1R) -1- (2,3-diphenylphenyl) ethyl-1-thio group, (1R) -1- (2,4-diphenylphenyl) ethyl-1-thio group (1R) -1- (2,5-diphenylphenyl) ethyl-1-thio group, (1R) -1- (2, 6-diphenylphenyl) ethyl-1-thio group, (1R) -1- (3,4-diphenylphenyl) ethyl-1-thio group, (1R) -1- (3,5-diphenylphenyl) ethyl-1 -Thio group, (1R) -1- (2,3,4-triphenylphen L) ethyl-1-thio group, (1R) -1- (2,3,5-triphenylphenyl) ethyl-1-thio group, (1R) -1- (2,3,6-triphenylphenyl) Ethyl-1-thio group, (1R) -1- (2,4,5-triphenylphenyl) ethyl-1-thio group, (1R) -1- (2,4,6-triphenylphenyl) ethyl- 1-thio group, (1R) -1- [2- (2-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2- (3-methylphenyl) phenyl] ethyl-1- Thio group, (1R) -1- [2- (4-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [3- (2-methylphenyl) phenyl] ethyl-1-thio group (1R) -1- [3- (3-methylphenyl) phenyl] ethyl-1-thio group, 1R) -1- [3- (4-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [4- (2-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [4- (3-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [4- (4-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1 -[(2,3-bis (2-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1-[(2,3-bis (3-methylphenyl) phenyl] ethyl-1-thio group (1R) -1-[(2,3-bis (4-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,4-bis (2-methylphenyl) phenyl] ethyl -1-thio group, (1R) -1- [2,4-bis (3-methylphenyl) phenol Nyl] ethyl-1-thio group, (1R) -1- [2,4-bis (4-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,5-bis (2 -Methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,5-bis (3-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,5 -Bis (4-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,6-bis (2-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,6-bis (3-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,6-bis (4-methylphenyl) phenyl] ethyl-1-thio group, (1R ) -1- [3,4-bis (2-methylphenyl) phenyl] ethyl-1-thio group, 1R) -1- [3,4-bis (3-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [3,4-bis (4-methylphenyl) phenyl] ethyl-1- Thio group, (1R) -1- [3,5-bis (2-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [3,5-bis (3-methylphenyl) phenyl] Ethyl-1-thio group, (1R) -1- [3,5-bis (4-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,3,4-tris (2 -Methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,3,4-tris (3-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2 , 3,4-Tris (4-methylphenyl) phenyl] ethyl-1-thio group, (1R) 1- [2,3,5-tris (2-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,3,5-tris (3-methylphenyl) phenyl] ethyl-1 -Thio group, (1R) -1- [2,3,5-tris (4-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,3,6-tris (2- Methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,3,6-tris (3-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2, 3,6-tris (4-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,4,5-tris (2-methylphenyl) phenyl] ethyl-1-thio group, 1R) -1- [2,4,5-tris (3-methylphenyl) phenyl] ethyl- 1-thio group, (1R) -1- [2,4,5-tris (4-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,4,6-tris (2 -Methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,4,6-tris (3-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2 , 4,6-tris (4-methylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,3,4-tris (4-tert-butylphenyl) phenyl] ethyl-1-thio Group, (1R) -1- [2,3,4-tris (4-tert-butylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,3,4-tris (4- tert-butylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,3 5-tris (4-tert-butylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,3,5-tris (4-tert-butylphenyl) phenyl] ethyl-1-thio group (1R) -1- [2,3,5-tris (4-tert-butylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,3,6-tris (4-tert -Butylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,3,6-tris (4-tert-butylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,3,6-tris (4-tert-butylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,4,5-tris (4-tert-butylphenyl) phenyl] ethyl -1-thio group, (1R) -1- [ , 4,5-tris (4-tert-butylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,4,5-tris (4-tert-butylphenyl) phenyl] ethyl-1 -Thio group, (1R) -1- [2,4,6-tris (4-tert-butylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,4,6-tris ( 4-tert-butylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2,4,6-tris (4-tert-butylphenyl) phenyl] ethyl-1-thio group, (1R) -1- [2- (1-naphthyl) phenyl] ethyl-1-thio group, (1R) -1- [3- (1-naphthyl) phenyl] ethyl-1-thio group, (1R) -1- [ 4- (1-naphthyl) phenyl] ethyl-1-thio group, (1R ) -1- [2,4-bis (1-naphthyl) phenyl] ethyl-1-thio group, (1R) -1- (2-methoxy-3-phenylphenyl) ethyl-1-thio group, (1R) -1- (2-methoxy-4-phenylphenyl) ethyl-1-thio group, (1R) -1- (2-methoxy-5-phenylphenyl) ethyl-1-thio group, (1R) -1- ( 2-methoxy-6-phenylphenyl) ethyl-1-thio group, (1R) -1- (2-isopropoxy-3-phenylphenyl) ethyl-1-thio group, (1R) -1- (2-iso Propoxy-4-phenylphenyl) ethyl-1-thio group, (1R) -1- (2-isopropoxy-5-phenylphenyl) ethyl-1-thio group, (1R) -1- (2-isopropoxy- 6-Phenylphenyl) ethyl-1-thio group (1R) -1- [2-methoxy-3- (1-naphthylphenyl] ethyl-1-thio group, (1R) -1- [2-methoxy-4- (1-naphthyl) phenyl] ethyl-1- Thio group, (1R) -1- [2-methoxy-5- (1-naphthyl) phenyl] ethyl-1-thio group, (1R) -1- [2-methoxy-6- (1-naphthyl) phenyl] Ethyl-1-thio group, (1R) -1- [2-isopropoxy-3- (1-naphthyl) phenyl] ethyl-1-thio group, (1R) -1- [2-isopropoxy-4- ( 1-naphthyl) phenyl] ethyl-1-thio group, (1R) -1- [2-isopropoxy-5- (1-naphthyl) phenyl] ethyl-1-thio group, (1R) -1- [2- Isopropoxy-6- (1-naphthyl) phenyl] ethyl-1-thio group, ( R) -1- (2-phenylphenyl) propyl-1-thio group, (1R) -1- (3-phenylphenyl) propyl-1-thio group, (1R) -1- (4-phenylphenyl) propyl -1-thio group, (1R) -1- (2,3-diphenylphenyl) propyl-1-thio group, (1R) -1- (2,4-diphenylphenyl) propyl-1-thio group, (1R ) -1- (2,5-diphenylphenyl) propyl-1-thio group, (1R) -1- (2,6-diphenylphenyl) propyl-1-thio group, (1R) -1- (3,4 -Diphenylphenyl) propyl-1-thio group, (1R) -1- (3,5-diphenylphenyl) propyl-1-thio group, (1R) -1- (2,3,4-triphenylphenyl) propyl -1-thio group, (1R) -1- (2,3 , 5-triphenylphenyl) propyl-1-thio group, (1R) -1- (2,3,6-triphenylphenyl) propyl-1-thio group, (1R) -1- (2,4,5 -Triphenylphenyl) propyl-1-thio group, (1R) -1- (2,4,6-triphenylphenyl) propyl-1-thio group, (1R) -1- [2- (2-methylphenyl) ) Phenyl] propyl-1-thio group, (1R) -1- [2- (3-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2- (4-methylphenyl) phenyl ] Propyl-1-thio group, (1R) -1- [3- (2-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [3- (3-methylphenyl) phenyl] propyl -1-thio group, (1R) -1- [3- (4-methyl) Phenyl) phenyl] propyl-1-thio group, (1R) -1- [4- (2-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [4- (3-methylphenyl) Phenyl] propyl-1-thio group, (1R) -1- [4- (4-methylphenyl) phenyl] propyl-1-thio group, (1R) -1-[(2,3-bis (2-methyl) Phenyl) phenyl] propyl-1-thio group, (1R) -1-[(2,3-bis (3-methylphenyl) phenyl] propyl-1-thio group, (1R) -1-[(2,3 -Bis (4-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,4-bis (2-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,4-bis (3-methylphenyl) phenyl] propi -1-thio group, (1R) -1- [2,4-bis (4-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,5-bis (2-methylphenyl) ) Phenyl] propyl-1-thio group, (1R) -1- [2,5-bis (3-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,5-bis ( 4-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,6-bis (2-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2, 6-bis (3-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,6-bis (4-methylphenyl) phenyl] propyl-1-thio group, (1R) -1 -[3,4-bis (2-methylphenyl) phenyl] propyl-1-thio Group, (1R) -1- [3,4-bis (3-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [3,4-bis (4-methylphenyl) phenyl] propyl -1-thio group, (1R) -1- [3,5-bis (2-methylphenyl) phenyl] propyl-1

-Thio group, (1R) -1- [3,5-bis (3-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [3,5-bis (4-methylphenyl) phenyl ] Propyl-1-thio group, (1R) -1- [2,3,4-tris (2-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,3,4- Tris (3-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,3,4-tris (4-methylphenyl) phenyl] propyl-1-thio group, (1R) -1 -[2,3,5-tris (2-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,3,5-tris (3-methylphenyl) phenyl] propyl-1- Thio group, (1R) -1- [2,3,5-tris (4-methylpheny ) Phenyl] propyl-1-thio group, (1R) -1- [2,3,6-tris (2-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,3, 6-tris (3-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,3,6-tris (4-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,4,5-tris (2-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,4,5-tris (3-methylphenyl) phenyl] propyl- 1-thio group, (1R) -1- [2,4,5-tris (4-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,4,6-tris (2 -Methylphenyl) phenyl] propyl-1-thio group, (1R) -1- 2,4,6-tris (3-methylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,4,6-tris (4-methylphenyl) phenyl] propyl-1-thio group (1R) -1- [2,3,4-tris (4-tert-butylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,3,4-tris (4-tert -Butylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,3,4-tris (4-tert-butylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,3,5-tris (4-tert-butylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,3,5-tris (4-tert-butylphenyl) phenyl] propyl -1-thio group, (1R) -1- [ 2,3,5-tris (4-tert-butylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,3,6-tris (4-tert-butylphenyl) phenyl] propyl- 1-thio group, (1R) -1- [2,3,6-tris (4-tert-butylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,3,6-tris (4-tert-butylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,4,5-tris (4-tert-butylphenyl) phenyl] propyl-1-thio group, (1R ) -1- [2,4,5-tris (4-tert-butylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,4,5-tris (4-tert-butylphenyl) ) Phenyl] propyl-1-thio (1R) -1- [2,4,6-tris (4-tert-butylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,4,6-tris (4-tert -Butylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2,4,6-tris (4-tert-butylphenyl) phenyl] propyl-1-thio group, (1R) -1- [2- (1-naphthyl) phenyl] propyl-1-thio group, (1R) -1- [3- (1-naphthyl) phenyl] propyl-1-thio group, (1R) -1- [4- ( 1-naphthyl) phenyl] propyl-1-thio group, (1R) -1- [2,4-bis (1-naphthyl) phenyl] propyl-1-thio group, (1R) -1- (2-methoxy- 3-phenylphenyl) propyl-1-thio group, (1R) -1- 2-methoxy-4-phenylphenyl) propyl-1-thio group, (1R) -1- (2-methoxy-5-phenylphenyl) propyl-1-thio group, (1R) -1- (2-methoxy-) 6-phenylphenyl) propyl-1-thio group, (1R) -1- (2-isopropoxy-3-phenylphenyl) propyl-1-thio group, (1R) -1- (2-isopropoxy-4- Phenylphenyl) propyl-1-thio group, (1R) -1- (2-isopropoxy-5-phenylphenyl) propyl-1-thio group, (1R) -1- (2-isopropoxy-6-phenylphenyl) ) Propyl-1-thio group, (1R) -1- [2-methoxy-3- (1-naphthylphenyl] propyl-1-thio group, (1R) -1- [2-methoxy-4- (1- Naphthyl) phenyl] Propyl-1-thio group, (1R) -1- [2-methoxy-5- (1-naphthyl) phenyl] propyl-1-thio group, (1R) -1- [2-methoxy-6- (1- Naphthyl) phenyl] propyl-1-thio group, (1R) -1- [2-isopropoxy-3- (1-naphthyl) phenyl] propyl-1-thio group, (1R) -1- [2-isopropoxy -4- (1-naphthyl) phenyl] propyl-1-thio group, (1R) -1- [2-isopropoxy-5- (1-naphthyl) phenyl] propyl-1-thio group, (1R) -1 -[2-Isopropoxy-6- (1-naphthyl) phenyl] propyl-1-thio group and the like can be mentioned.

  Although it does not specifically limit as a manufacturing method of the optically active ruthenium complex shown by the said General formula (1) of this invention, For example, it can manufacture simply with the following method.

That is,
(1) Tetrakis [pentamethylcyclopentadienylruthenium chloride] (Cp ^* RuCl) ₄ [where Cp ^* represents η ⁵ -C ₅ Me ₅ (pentamethylcyclopentadiene). ] And the following general formula (3)

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
It can prepare by making the disulfide shown by react.

  In this case, it is preferable to react tetrakis [pentamethylcyclopentadienylruthenium chloride] and the above-mentioned disulfide in a solvent inert to the reaction such as THF in the temperature range of 0 ° C. to 100 ° C. for 2 to 24 hours. .

  As a synthesis method of the disulfides represented by the general formula (3), the following general formula (5)

(In the above formula, R ₃ is a phenyl group in which the nucleus is substituted with 1 to 5 nuclei, a phenyl group in which the nucleus is substituted with 1 to 5 in the substituted phenyl group, or a phenyl group in which the nucleus is substituted with 1 to 5 in the naphthyl group A phenyl group in which the nucleus is substituted by 1 to 5 with a substituted naphthyl group, a 2-alkoxyphenyl group in which the nucleus is substituted by 1 to 4 by a phenyl group, or a 2-alkoxyphenyl group in which the nucleus is substituted by 1 to 4 by a substituted phenyl group And a 2-alkoxyphenyl group in which the nucleus is substituted by 1 to 4 with a naphthyl group or a 2-alkoxyphenyl group in which the nucleus is substituted by 1 to 4 with a substituted naphthyl group
An asymmetric alkylation reaction is performed on the aldehydes represented by the following general formula (4):

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
After obtaining an optically active alcohol represented by the following formula, an acetylthio group is introduced by an inversion reaction, then an optically active thiol is obtained by reduction, and further oxidized to obtain a disulfide represented by the above general formula (3). it can.

In the present invention, the disulfides represented by the general formula (3) specifically include (R, R) -bis [1- (2-phenylphenyl) -1-ethyl] disulfide, (R, R ) -Bis [1- (3-phenylphenyl) -1-ethyl] disulfide, (R, R) -bis [1- (4-phenylphenyl) -1-ethyl] disulfide, (R, R) -bis [ 1- (2,3-diphenylphenyl) -1-ethyl] disulfide, (R, R) -bis [1- (2,4-diphenylphenyl) -1-ethyl] disulfide, (R, R) -bis [ 1- (2,5-diphenylphenyl) -1-ethyl] disulfide, (R, R) -bis [1- (2,6-diphenylphenyl) -1-ethyl] disulfide, (R, R) -bis [ 1- (3,4-diphenylphenol L) -1-ethyl] disulfide, (R, R) -bis [1- (3,5-diphenylphenyl) -1-ethyl] disulfide, (R, R) -bis [1- (2,3,4) -Triphenylphenyl) -1-ethyl] disulfide, (R, R) -bis [1- (2,3,5-triphenylphenyl) -1-ethyl] disulfide, (R, R) -bis [1- (2,3,6-triphenylphenyl) -1-ethyl] disulfide, (R, R) -bis [1- (2,4,5-triphenylphenyl) -1-ethyl] disulfide, (R, R ) -Bis [1- (2,4,6-triphenylphenyl) -1-ethyl] disulfide, (R, R) -bis {1- [2- (2-methylphenyl) phenyl] -1-ethyl} Disulfide, (R, R) -bis {1- [2- (3- Tilphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2- (4-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [ 3- (2-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [3- (3-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -Bis {1- [3- (4-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [4- (2-methylphenyl) phenyl] -1-ethyl} disulfide , (R, R) -bis {1- [4- (3-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [4- (4-methylphenyl) phenyl] -1-ethyl} disulfide , (R, R) -bis {1-[(2,3-di (2-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1-[(2,3-di (3-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1-[(2,3-di (4-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) R) -bis {1- [2,4-di (2-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,4-di (3-methylphenyl) Phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,4-di (4-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,5-di (2-methylphenyl) phenyl] -1-ethyl} disulfide, R, R) -bis {1- [2,5-di (3-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,5-di (4-methyl) Phenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,6-di (2-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis { 1- [2,6-di (3-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,6-di (4-methylphenyl) phenyl] -1- Ethyl} disulfide, (R, R) -bis {1- [3,4-di (2-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [3,4- Di (3-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R -Bis {1- [3,4-di (4-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [3,5-di (2-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [3,5-di (3-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [3 , 5-di (4-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,3,4-tri (2-methylphenyl) phenyl] -1-ethyl} Disulfide, (R, R) -bis {1- [2,3,4-tri (3-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,3, 4-tri (4-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,3,5-tri (2-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,3,5- Tris (3-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,3,5-tri (4-methylphenyl) phenyl] -1-ethyl} disulfide, ( R, R) -bis {1- [2,3,6-tri (2-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,3,6-tri (3-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,3,6-tri (4-methylphenyl) phenyl] -1-ethyl} disulfide, (R , R) -bis {1- [2,4,5-tri (2-methylphenyl) fur Nyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,4,5-tri (3-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis { 1- [2,4,5-tri (4-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,4,6-tri (2-methylphenyl) phenyl ] -1-ethyl} disulfide, (R, R) -bis {1- [2,4,6-tri (3-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1 -[2,4,6-tri (4-methylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,3,4-tri (4-tert-butylphenyl) Phenyl] -1-ethyl} disulfide, (R, R) -bis {1 [2,3,5-tri (4-tert-butylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,3,6-tri (4-tert-butylphenyl) ) Phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,3,6-tri (4-tert-butylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -Bis {1- [2,4,5-tris (4-tert-butylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,4,6-tris (4 -Tert-butylphenyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2- (1-naphthyl) phenyl] -1-ethyl} disulfide, (R, R) -bis { 1- [3- (1-naphthyl) phenyl ] -1-ethyl} disulfide, (R, R) -bis {1- [4- (1-naphthyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2,4- Di (1-naphthyl) phenyl] -1-ethyl} disulfide, (R, R) -bis [1- (2-methoxy-3-phenylphenyl) -1-ethyl] disulfide, (R, R) -bis [ 1- (2-methoxy-4-phenylphenyl) -1-ethyl] disulfide, (R, R) -bis [1- (2-methoxy-5-phenylphenyl) -1-ethyl] disulfide, (R, R ) -Bis [1- (2-methoxy-6-phenylphenyl) -1-ethyl] disulfide, (R, R) -bis [1- (2-isopropoxy-3-phenylphenyl) -1-ethyl] disulfide , (R, R) -bis [1 (2-isopropoxy-4-phenylphenyl) -1-ethyl] disulfide, (R, R) -bis [1- (2-isopropoxy-5-phenylphenyl) -1-ethyl] disulfide, (R, R ) -Bis [1- (2-isopropoxy-6-phenylphenyl) -1-ethyl] disulfide, (R, R) -bis {1- [2-methoxy-3- (1-naphthyl) phenyl] -1 -Ethyl} disulfide, (R, R) -bis {1- [2-methoxy-4- (1-naphthyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2-methoxy -5- (1-naphthyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2-methoxy-6- (1-naphthyl) phenyl] -1-ethyl} disulfide, (R , R) -bis {1 [2-Isopropoxy-3- (1-naphthyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2-isopropoxy-4- (1-naphthyl) phenyl] -1- Ethyl} disulfide, (R, R) -bis {1- [2-isopropoxy-5- (1-naphthyl) phenyl] -1-ethyl} disulfide, (R, R) -bis {1- [2-iso Propoxy-6- (1-naphthyl) phenyl] -1-ethyl} disulfide, (R, R) -bis [1- (2-phenylphenyl) -1-propyl] disulfide, (R, R) -bis [1 -(3-phenylphenyl) -1-propyl] disulfide, (R, R) -bis [1- (4-phenylphenyl) -1-propyl] disulfide, (R, R) -bis [1- (2, 3-diphenylphenyl) -1-propyl] disulfide, (R, R) -bis [1- (2,4-diphenylphenyl) -1-propyl] disulfide, (R, R) -bis [1- (2,5-diphenylphenyl) -1-propyl] disulfide, (R, R) -bis [1- (2,6-diphenylphenyl) -1-propyl] disulfide, (R, R) -bis [1- (3,4-diphenylphenyl) -1-propyl] disulfide, (R, R) -bis [1- (3,5-diphenylphenyl) -1-propyl] disulfide, (R, R) -bis [1- (2,3,4-tri Phenylphenyl) -1-propyl] disulfide, (R, R) -bis [1- (2,3,5-triphenylphenyl) -1-propyl] disulfide, (R, R) -bis [1- (2 , 3,6-Triphenylphenol Nyl) -1-propyl] disulfide, (R, R) -bis [1- (2,4,5-triphenylphenyl) -1-propyl] disulfide, (R, R) -bis [1- (2, 4,6-triphenylphenyl) -1-propyl] disulfide, (R, R) -bis {1- [2- (2-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2- (3-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2- (4-methylphenyl) phenyl] -1-propyl} disulfide, ( R, R) -bis {1- [3- (2-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [3- (3-methylphenyl) phenyl] -1 -Propyl} disulfide, ( , R) -bis {1- [3- (4-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [4- (2-methylphenyl) phenyl] -1- Propyl} disulfide, (R, R) -bis {1- [4- (3-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [4- (4-methylphenyl) ) Phenyl] -1-propyl} disulfide, (R, R) -bis {1-[(2,3-di (2-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis { 1-[(2,3-di (3-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1-[(2,3-di (4-methylphenyl) phenyl]- 1-propyl} disulfide, (R, R) -bis {1- [2,4-di (2-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,4-di (3-methylphenyl) phenyl] -1 -Propyl} disulfide, (R, R) -bis {1- [2,4-di (4-methylphenyl) phenyl

] -1-propyl} disulfide, (R, R) -bis {1- [2,5-di (2-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [ 2,5-di (3-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,5-di (4-methylphenyl) phenyl] -1-propyl} disulfide , (R, R) -bis {1- [2,6-di (2-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,6-di (3 -Methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,6-di (4-methylphenyl) phenyl] -1-propyl} disulfide, (R, R)- Bis {1- [3,4-di (2-methylphenyl) phenyl Nyl] -1-propyl} disulfide, (R, R) -bis {1- [3,4-di (3-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [3,4-di (4-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [3,5-di (2-methylphenyl) phenyl] -1-propyl} Disulfide, (R, R) -bis {1- [3,5-di (3-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [3,5-di ( 4-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,3,4-tri (2-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) R) -bis {1- [2,3,4-tri (3- Tilphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,3,4-tri (4-methylphenyl) phenyl] -1-propyl} disulfide, (R, R)- Bis {1- [2,3,5-tri (2-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,3,5-tris (3-methylphenyl) ) Phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,3,5-tri (4-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,3,6-tri (2-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,3,6-tri (3-methylphenyl) Phenyl] -1-propyl} disulfide , (R, R) -bis {1- [2,3,6-tri (4-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,4,5 -Tri (2-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,4,5-tri (3-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,4,5-tri (4-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,4,6- Tri (2-methylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,4,6-tri (3-methylphenyl) phenyl] -1-propyl} disulfide, ( R, R) -bis {1- [2,4,6-tri (4-methyl) Phenyl) -1-propyl} disulfide, (R, R) -bis {1- [2,3,4-tri (4-tert-butylphenyl) phenyl] -1-propyl} disulfide, (R, R) ) -Bis {1- [2,3,5-tri (4-tert-butylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,3,6-tri ( 4-tert-butylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,3,6-tri (4-tert-butylphenyl) phenyl] -1-propyl} disulfide , (R, R) -bis {1- [2,4,5-tris (4-tert-butylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2,4 , 6-Tris (4-ter -Butylphenyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2- (1-naphthyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [3- (1-naphthyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [4- (1-naphthyl) phenyl] -1-propyl} disulfide, (R, R)- Bis {1- [2,4-di (1-naphthyl) phenyl] -1-propyl} disulfide, (R, R) -bis [1- (2-methoxy-3-phenylphenyl) -1-propyl] disulfide , (R, R) -bis [1- (2-methoxy-4-phenylphenyl) -1-propyl] disulfide, (R, R) -bis [1- (2-methoxy-5-phenylphenyl) -1 -Propyl] disulfi (R, R) -bis [1- (2-methoxy-6-phenylphenyl) -1-propyl] disulfide, (R, R) -bis [1- (2-isopropoxy-3-phenylphenyl) -1-propyl] disulfide, (R, R) -bis [1- (2-isopropoxy-4-phenylphenyl) -1-propyl] disulfide, (R, R) -bis [1- (2-isopropoxy) -5-phenylphenyl) -1-propyl] disulfide, (R, R) -bis [1- (2-isopropoxy-6-phenylphenyl) -1-propyl] disulfide, (R, R) -bis {1 -[2-methoxy-3- (1-naphthyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2-methoxy-4- (1-naphthyl) phenyl] -1-propyl } (R, R) -bis {1- [2-methoxy-5- (1-naphthyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2-methoxy-6] -(1-naphthyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2-isopropoxy-3- (1-naphthyl) phenyl] -1-propyl} disulfide, (R, R) R) -bis {1- [2-isopropoxy-4- (1-naphthyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2-isopropoxy-5- (1- Naphthyl) phenyl] -1-propyl} disulfide, (R, R) -bis {1- [2-isopropoxy-6- (1-naphthyl) phenyl] -1-propyl} disulfide, and the like.

Specific examples of the optically active alcohol represented by the general formula (4) include (S) -1- (2-phenylphenyl) -1-ethanol and (S) -1- (3-phenyl). Phenyl) -1-ethanol, (S) -1- (4-phenylphenyl) -1-ethanol, (S) -1- (2,3-diphenylphenyl) -1-ethanol, (S) -1- ( 2,4-diphenylphenyl) -1-ethanol, (S) -1- (2,5-diphenylphenyl) -1-ethanol, (S) -1- (2,6-diphenylphenyl) -1-ethanol, (S) -1- (3,4-diphenylphenyl) -1-ethanol, (S) -1- (3,5-diphenylphenyl) -1-ethanol, (S) -1- (2,3,4) -Triphenylphenyl) -1-ethanol, (S -1- (2,3,5-triphenylphenyl) -1-ethanol, (S) -1- (2,3,6-triphenylphenyl) -1-ethanol, (S) -1- (2, 4,5-triphenylphenyl) -1-ethanol, (S) -1- (2,4,6-triphenylphenyl) -1-ethanol, (S) -1- [2- (2-methylphenyl) Phenyl] -1-ethanol, (S) -1- [2- (3-methylphenyl) phenyl] -1-ethanol, (S) -1- [2- (4-methylphenyl) phenyl] -1-ethanol (S) -1- [3- (2-methylphenyl) phenyl] -1-ethanol, (S) -1- [3- (3-methylphenyl) phenyl] -1-ethanol, (S) -1 -[3- (4-Methylphenyl) phenyl] -1-ethanol (S) -1- [4- (2-methylphenyl) phenyl] -1-ethanol, (S) -1- [4- (3-methylphenyl) phenyl] -1-ethanol, (S) -1- [4- (4-Methylphenyl) phenyl] -1-ethanol, (S) -1-[(2,3-di (2-methylphenyl) phenyl] -1-ethanol, (S) -1-[( 2,3-di (3-methylphenyl) phenyl] -1-ethanol, (S) -1-[(2,3-di (4-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,4-di (2-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,4-di (3-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,4-di (4-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,5-di (2-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,5-di (3-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,5-di (4-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,6-di (2-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,6-di (3-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,6-di (4-methylphenyl) phenyl] -1-ethanol, (S) -1- [3,4-di (2-methylphenyl) phenyl] -1-ethanol, (S) -1- [3,4-di (3-methylphenyl) phenyl] -1-ethanol, (S) -1- [3,4-di (4-methylphenyl) phenyl] -1-ethanol, (S) -1- 3,5-di (2-methylphenyl) phenyl] -1-ethanol, (S) -1- [3,5-di (3-methylphenyl) phenyl] -1-ethanol, (S) -1- [ 3,5-di (4-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,3,4-tri (2-methylphenyl) phenyl] -1-ethanol, (S) -1 -[2,3,4-tri (3-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,3,4-tri (4-methylphenyl) phenyl] -1-ethanol, ( S) -1- [2,3,5-tri (2-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,3,5-tris (3-methylphenyl) pheni] -1 -Ethanol, (S) -1- [2,3,5-tri (4-methylphenyl) phen L] -1-ethanol, (S) -1- [2,3,6-tri (2-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,3,6-tri (3 -Methylphenyl) phenyl] -1-ethanol, (S) -1- [2,3,6-tri (4-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,4,5 -Tri (2-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,4,5-tri (3-methylphenyl) phenyl] -1-ethanol, (S) -1- [2 , 4,5-tri (4-methylphenyl) pheni] -1-ethanol, (S) -1- [2,4,6-tri (2-methylphenyl) phenyl] -1-ethanol, (S)- 1- [2,4,6-tri (3-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,4,6-tri (4-methylphenyl) phenyl] -1-ethanol, (S) -1- [2,3,4-tri (4-tert-butylphenyl) phenyl] -1 -Ethanol, (S) -1- [2,3,5-tri (4-tert-butylphenyl) phenyl] -1-ethanol, (S) -1- [2,3,6-tri (4-tert -Butylphenyl) phenyl] -1-ethanol, (S) -1- [2,3,6-tri (4-tert-butylphenyl) phenyl] -1-ethanol, (S) -1- [2,4 , 5-tris (4-tert-butylphenyl) phenyl] -1-ethanol, (S) -1- [2,4,6-tris (4-tert-butylphenyl) phenyl] -1-ethanol, (S ) -1- [2- (1-naphthyl) phenyl] -1 Ethanol, (S) -1- [3- (1-naphthyl) phenyl] -1-ethanol, (S) -1- [4- (1-naphthyl) phenyl] -1-ethanol, (S) -1- [2,4-di (1-naphthyl) phenyl] -1-ethanol, (S) -1- (2-methoxy-3-phenylphenyl) -1-ethanol, (S) -1- (2-methoxy- 4-phenylphenyl) -1-ethanol, (S) -1- (2-methoxy-5-phenylphenyl) -1-ethanol, (S) -1- (2-methoxy-6-phenylphenyl) -1- Ethanol, (S) -1- (2-isopropoxy-3-phenylphenyl) -1-ethanol, (S) -1- (2-isopropoxy-4-phenylphenyl) -1-ethanol, (S)- 1- (2-Isopropoxy-5-thio Nylphenyl) -1-ethanol, (S) -1- (2-isopropoxy-6-phenylphenyl) -1-ethanol, (S) -1- [2-methoxy-3- (1-naphthylphenyl] -1 -Ethanol, (S) -1- [2-methoxy-4- (1-naphthyl) phenyl] -1-ethanol, (S) -1- [2-methoxy-5- (1-naphthyl) phenyl] -1 -Ethanol, (S) -1- [2-methoxy-6- (1-naphthyl) phenyl] -1-ethanol, (S) -1- [2-isopropoxy-3- (1-naphthyl) phenyl]- 1-ethanol, (S) -1- [2-isopropoxy-4- (1-naphthyl) phenyl] -1-ethanol, (S) -1- [2-isopropoxy-5- (1-naphthyl) phenyl ] -1-ethanol, (S) -1- [2-Isopropoxy-6- (1-naphthyl) phenyl] -1-ethanol, (S) -1- (2-phenylphenyl) -1-propanol, (S) -1- (3-phenylphenyl)- 1-propanol, (S) -1- (4-phenylphenyl) -1-propanol, (S) -1- (2,3-diphenylphenyl) -1-propanol, (S) -1- (2,4 -Diphenylphenyl) -1-propanol, (S) -1- (2,5-diphenylphenyl) -1-propanol, (S) -1- (2,6-diphenylphenyl) -1-propanol, (S) -1- (3,4-diphenylphenyl) -1-propanol, (S) -1- (3,5-diphenylphenyl) -1-propanol, (S) -1- (2,3,4-triphenyl) Phenyl) -1-p Panol, (S) -1- (2,3,5-triphenylphenyl) -1-propanol, (S) -1- (2,3,6-triphenylphenyl) -1-propanol, (S)- 1- (2,4,5-triphenylphenyl) -1-propanol, (S) -1- (2,4,6-triphenylphenyl) -1-propanol, (S) -1- [2- ( 2-methylphenyl) phenyl] -1-propanol, (S) -1- [2- (3-methylphenyl) phenyl] -1-propanol, (S) -1- [2- (4-methylphenyl) phenyl ] -1-propanol, (S) -1- [3- (2-methylphenyl) phenyl] -1-propanol, (S) -1- [3- (3-methylphenyl) phenyl] -1-propanol, (S) -1- [3- (4-Methylphen Nyl) phenyl] -1-propanol, (S) -1- [4- (2-methylphenyl) phenyl] -1-propanol, (S) -1- [4- (3-methylphenyl) phenyl] -1 -Propanol, (S) -1- [4- (4-methylphenyl) phenyl] -1-propanol, (S) -1-[(2,3-di (2-methylphenyl) phenyl] -1-propanol , (S) -1-[(2,3-di (3-methylphenyl) phenyl] -1-propanol, (S) -1-[(2,3-di (4-methylphenyl) phenyl] -1 -Propanol, (S) -1- [2,4-di (2-methylphenyl) phenyl] -1-propanol, (S) -1- [2,4-di (3-methylphenyl) phenyl] -1 -Propanol, (S) -1- [2,4-di (4-methyl) Ruphenyl) phenyl] -1-propanol, (S) -1- [2,5-di (2-methylphenyl) phenyl] -1-propanol, (S) -1- [2,5-di (3-methyl) Phenyl) phenyl] -1-propanol, (S) -1- [2,5-di (4-methylphenyl) phenyl] -1-propanol, (S) -1- [2,6-di (2-methyl) Phenyl) phenyl] -1-propanol, (S) -1- [2,6-di (3-methylphenyl) phenyl] -1-propanol, (S) -1- [2,6-di (4-methyl) Phenyl) phenyl] -1-propanol, (S) -1- [3,4-di (2-methylphenyl) phenyl] -1-propanol, (S) -1- [3,4-di (3-methyl) Phenyl) phenyl] -1-propanol, (S) -1- [3 4-di (4-methylphenyl) phenyl] -1-propanol, (S) -1- [3,5-di (2-methylphenyl) phenyl] -1-propanol, (S) -1- [3 5-di (3-methylphenyl) phenyl] -1-propanol, (S) -1- [3,5-di (4-methylphenyl) phenyl] -1-propanol, (S) -1- [2, 3,4-tri (2-methylphenyl) phenyl] -1-propanol, (S) -1- [2,3,4-tri (3-methylphenyl) phenyl] -1-propanol, (S) -1 -[2,3,4-tri (4-methylphenyl) phenyl] -1-propanol, (S) -1- [2,3,5-tri (2-methylphenyl) phenyl] -1-propanol, S) -1- [2,3,5-Tris (3-methylpheny ) Pheni] -1-propanol, (S) -1- [2,3,5-tri (4-methylphenyl) phenyl] -1-propanol, (S) -1- [2,3,6-tri ( 2-methylphenyl) phenyl] -1-propanol, (S) -1- [2,3,6-tri (3-methylphenyl) phenyl] -1-propanol, (S) -1- [2,3, 6-tri (4-methylphenyl) phenyl] -1-propanol, (S) -1- [2,4,5-tri (2-methylphenyl) phenyl] -1-propanol, (S) -1- [ 2,4,5-tri (3-methylphenyl) phenyl] -1-propanol, (S) -1- [2,4,5-tri (4-methylphenyl) pheni] -1-propanol, (S) -1- [2,4,6-tri (2-methylphenyl) phenyl]- 1-propanol, (S) -1- [2,4,6-tri (3-methylphenyl) phenyl] -1-propanol, (S) -1- [2,4,6-tri (4-methylphenyl) ) Phenyl] -1-propanol, (S) -1- [2,3,4-tri (4-tert-butylpheny)

L) phenyl] -1-propanol, (S) -1- [2,3,5-tri (4-tert-butylphenyl) phenyl] -1-propanol, (S) -1- [2,3,6 -Tri (4-tert-butylphenyl) phenyl] -1-propanol, (S) -1- [2,3,6-tri (4-tert-butylphenyl) phenyl] -1-propanol, (S)- 1- [2,4,5-tris (4-tert-butylphenyl) phenyl] -1-propanol, (S) -1- [2,4,6-tris (4-tert-butylphenyl) phenyl]- 1-propanol, (S) -1- [2- (1-naphthyl) phenyl] -1-propanol, (S) -1- [3- (1-naphthyl) phenyl] -1-propanol, (S)- 1- [4- (1-naphthyl) pheny ] -1-propanol, (S) -1- [2,4-di (1-naphthyl) phenyl] -1-propanol, (S) -1- (2-methoxy-3-phenylphenyl) -1-propanol (S) -1- (2-methoxy-4-phenylphenyl) -1-propanol, (S) -1- (2-methoxy-5-phenylphenyl) -1-propanol, (S) -1- ( 2-methoxy-6-phenylphenyl) -1-propanol, (S) -1- (2-isopropoxy-3-phenylphenyl) -1-propanol, (S) -1- (2-isopropoxy-4- Phenylphenyl) -1-propanol, (S) -1- (2-isopropoxy-5-phenylphenyl) -1-propanol, (S) -1- (2-isopropoxy-6-phenylphenyl) -1- The Panol, (S) -1- [2-methoxy-3- (1-naphthylphenyl) -1-propanol, (S) -1- [2-methoxy-4- (1-naphthyl) phenyl] -1-propanol (S) -1- [2-methoxy-5- (1-naphthyl) phenyl] -1-propanol, (S) -1- [2-methoxy-6- (1-naphthyl) phenyl] -1-propanol , (S) -1- [2-isopropoxy-3- (1-naphthyl) phenyl] -1-propanol, (S) -1- [2-isopropoxy-4- (1-naphthyl) phenyl] -1 -Propanol, (S) -1- [2-isopropoxy-5- (1-naphthyl) phenyl] -1-propanol, (S) -1- [2-isopropoxy-6- (1-naphthyl) phenyl] -1-propanol and the like The

  The optically active ruthenium complex represented by the general formula (1) of the present invention may be isolated and identified after preparation and used as it is as a catalyst for an asymmetric synthesis reaction, or immediately after the post-treatment, the asymmetric synthesis reaction. You may use as a catalyst for this. The post-treatment method after completion of the reaction is not particularly limited, but a stable catalyst can be obtained by distilling off the solvent, extracting with dichloromethane and then recrystallizing. For unstable catalysts, it is preferable to distill off the solvent after completion of the reaction and use it in the next reaction as it is.

  As an example of using the optically active ruthenium complex of the present invention as an asymmetric synthesis reaction catalyst, the following general formula (6)

(In the formula, R ₄ is a linear or branched alkyl group having 1 to 10 carbon atoms, phenyl group, 1-naphthyl group, 2-naphthyl group, cycloalkyl group having 3 to 8 carbon atoms, or 1 to 5 carbon atoms. A phenyl group in which the nucleus is substituted by 1 to 5 with a linear or branched alkyl group, a phenyl group in which the nucleus is substituted with a linear or branched alkyloxy group having 1 to 5 carbon atoms, and a nucleus with halogen. 1- to 5-substituted phenyl group, 1-naphthyl group having 1 to 5 carbon atoms and a linear or branched alkyl group having 1 to 5 carbon atoms, linear or branched alkyloxy group having 1 to 5 carbon atoms 1-naphthyl group in which the nucleus is substituted with 1 to 5 in the nucleus, 1-naphthyl group in which the nucleus is substituted with 1 to 5 in the halogen, or a linear or branched alkyl group having 1 to 5 carbon atoms is substituted with 1 to 5 in the nucleus 2-naphthyl group, straight chain having 1 to 5 carbon atoms Represents a 2-naphthyl group in which the nucleus is substituted by 1 to 5 with a branched alkyloxy group or a 2-naphthyl group in which the nucleus is substituted with 1 to 5 by halogen.
And propargyl alcohol represented by the following general formula (7)

(Wherein R ₅ and R ₆ are each independently hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkynyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. A linear or branched alkenyl group, a phenyl group, a benzyl group, a 1-naphthyl group, a 2-naphthyl group, a phenyl group in which a nucleus is substituted with a linear or branched alkyl group having 1 to 5 carbon atoms, A phenyl group in which the nucleus is substituted by 1 to 5 carbon atoms with a linear or branched alkoxy group having 1 to 5 carbon atoms, a phenyl group in which the nucleus is substituted by 1 to 5 carbon atoms with a halogen atom, a linear or branched chain having 1 to 5 carbon atoms 1-naphthyl group having 1-5 substituted nucleus with alkyl group, 1-naphthyl group having 1-5 substituted nucleus with straight chain or branched alkoxy group having 1-5 carbon atoms, 1-naphthyl group having 1 atom substituted with halogen atom 5-substituted 1-naphthyl group, carbon 2-naphthyl group in which the nucleus is substituted with 1 to 5 with a linear or branched alkyl group of 1 to 5, or 2-naphthyl with the nucleus 1 to 5 substituted with a linear or branched alkoxy group with 1 to 5 carbon atoms A 2-naphthyl group having a nucleus or a halogen atom substituted with 1 to 5 nuclei.)
Is reacted with a ketone represented by the following general formula (8):

(Wherein R ₄ , R ₅ and R ₆ have the same definition as above, and * represents an asymmetric carbon.)
The method for obtaining the ketone derivative represented by will be described below.

  In the method of the present invention, the compound represented by the general formula (6) is not particularly limited. Specifically, 3-butyn-2-ol, 1-pentyn-3-ol, 4- Methyl-1-pentyn-3-ol, 4,4-dimethyl-1-pentyn-3-ol, 1-hexyn-3-ol, 1-octin-3-ol, 1-cyclohexyl-2-propyne-1- Ol, 1-phenyl-2-propyn-1-ol, 1- (2-methylphenyl) -2-propyn-1-ol, 1- (3-methylphenyl) -2-propyn-1-ol, 1- (4-methylphenyl) -2-propyn-1-ol, 1- (2-chlorophenyl) -2-propyne-1-ol, 1- (3-chlorophenyl) -2-propyne-1-ol, 1- ( 4-chloropheny ) -2-propyn-1-ol, 1- (1-naphthyl) -2-propyne-1-ol, 1- (2-naphthyl) -2-propyn-1-ol, and other propargyl alcohols. .

  In the method of the present invention, the compound represented by the general formula (7) is not particularly defined. For example, acetone, methyl ethyl ketone, methyl tert-butyl ketone, methyl vinyl ketone, diethyl ketone, acetophenone, 1-naphthophenone And ketones such as 2-naphthophenone.

  As the compound represented by the general formula (8) produced by the method of the present invention, a propargyl alcohol represented by the general formula (6) and a ketone represented by the general formula (7) are reacted. Any compound can be used as long as it is a compound obtained and is not particularly limited. For example, 4-methyl-5-hexyn-2-one, 4-isopropyl-5-hexyn-2-one, 4-phenyl- 5-hexyn-2-one, 4- (1-naphthyl) -5-hexyn-2-one, 4- (2-naphthyl) -5-hexyn-2-one and the like can be mentioned.

  In the method of the present invention, the amount of the optically active ruthenium complex used in the asymmetric synthesis reaction is not particularly limited, but is usually 0.1 to 50 mol% with respect to the propargyl alcohols included in the reaction. The

  The solvent applicable to the method of the present invention is not particularly limited as long as it is an inert solvent for the reaction. If the ketones included in the reaction are liquid at the reaction temperature in the asymmetric synthesis reaction, the ketones may be used as a solvent.

  In the method of the present invention, the reaction temperature and time vary depending on the type of substrate provided for the reaction, and thus are not particularly limited, but the reaction is usually completed at −20 ° C. to 100 ° C. for 1 to 96 hours. .

In the method of the present invention, after completion of the reaction, the solvent is distilled off and then purified by a conventional method such as silica gel thin layer chromatography or column chromatography to obtain a product.
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Preparation of (S) -1- (2,3,5-triphenylphenyl) -1-propanol To a flask, add (1R) -trans-N, N′-cyclohexanediylbis (trifluoromethanesulfonamide (88.5 mg, 0.234 mmol), toluene (6 ml) and tetra (2-propoxy) titanium [IV] (665 mg, 2.34 mmol) were added and stirred for 20 minutes at 40 ° C. This was cooled to −78 ° C. A hexane solution (1.0 M, 14 ml, 14 mmol) was added, and then 2,3,5-triphenylbenzaldehyde (3.91 g, 11.7 mmol) was added, followed by raising the temperature to 0 ° C. for 4 hours. .

  After completion of the reaction, hydrochloric acid (1M) was added and separated, and the aqueous layer was extracted with diethyl ether. The obtained organic layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The obtained residue was purified by flash column chromatography using silica gel to obtain the desired product (S) -1- (2,3,5-triphenylphenyl) -1-propanol as a white solid ( 2.84 g, 7.8 mmol, 67% yield). The optical purity of the obtained target product was 92% ee as a result of measurement by high performance liquid chromatography (Eluent Hexane / 2-propanol = 96/4 vol / vol) using Daicel's Chiral Pack OD.

Appearance: White solid
¹ H-NMR (CDCl ₃ ) δ 0.83 (t, 3H, J = 7.6 Hz), 1.74 (dq, 1H, J = 7.6 and 6.6 Hz), 1.84 (d, 1H, J = 2.6 Hz), 4.62 (dt, 1 H, J = 2.6 and 6.6 Hz), 6.97-7.48 (m, 13 H), 7.56 (d, J = 2.0 Hz) ), 7.68-7.72 (m, 2H), 7.89 (d, 1H, J = 2.0 Hz).

¹³ C-NMR (CDCl ₃ ) δ 10.6, 31.7, 72.1, 123.3, 126.2, 126.6, 127.1, 127.3, 127.4, 127.6, 127. 7, 127.8, 128.7, 129.7, 130.3, 130.9, 138.1, 138.6, 140.4, 140.6141.6, 142.1, 143.4.

HRMS calculated value C ₂₇ H ₂₄ O [M]: 364.1827, measured value: 364.1826.

Preparation of (R, R) -bis [1- (2,3,5-triphenylphenyl) -1-propyl] disulfide Into a 100 ml flask was added triphenylphosphine (4.20 g, 16 mmol) and tetrahydrofuran (hereinafter, (Abbreviated as THF, 40 ml) was added, and the mixture was brought to 0 ° C. with stirring, and diisopropyl azodicarboxylate (40% toluene solution, 8.6 ml, 16 mmol) was added dropwise thereto. After stirring at 0 ° C. for 30 minutes, (S) -1- (2,3,5-triphenylphenyl) -1-propanol (2.84 g, 7.8 mmol) obtained in Example 1 and thioacetic acid ( A solution of 1.13 ml, 16 mmol) in THF (20 ml) was added dropwise, followed by reaction at room temperature for 12 hours. After completion of the reaction, the residue was washed with a saturated aqueous sodium hydrogen carbonate solution, and the resulting organic layer was dried over magnesium sulfate, filtered, and concentrated to obtain a residue. The obtained residue was purified by flash column chromatography using silica gel to obtain (R) -1- (2,3,5-triphenylphenyl) -1-propyl thioacetate (1.48 g, 3.5 mmol). Yield 45%) as a white solid.

  A solution of lithium aluminum hydride (394 mg, 10.5 mmol) in diethyl ether (20 ml) was brought to 0 ° C., and (R) -1- (2,3,5-triphenylphenyl) -1-propyl thioacetate ( A solution of diethyl ether (10 ml) of 1.48 g, 3.5 mmol) was added dropwise, and then reacted at room temperature for 12 hours. After completion of the reaction, the residue was washed with hydrochloric acid (1M), washed with water, dried over magnesium sulfate, filtered and concentrated to obtain a residue. By purifying the obtained residue by flash column chromatography using silica gel, (R) -1- (2,3,5-triphenylphenyl) -1-propylthiol (727 mg, 1.91 mmol, yield) 55%).

  At room temperature, a solution of (R) -1- (2,3,5-triphenylphenyl) -1-propylthiol (727 mg, 1.91 mmol) in methanol (20 ml) in iodine (727 mg, 2.87 mmol) in methanol ( 20 ml) After the solution was added dropwise, the reaction was carried out at room temperature for 12 hours. After completion of the reaction, sodium thiosulfate (10% aqueous solution) was added until the color of the solution disappeared, then extracted with dichloromethane, and the resulting organic layer was dried over magnesium sulfate, filtered, and concentrated to obtain a residue. It was. The obtained residue was purified by flash column chromatography using silica gel and recrystallized from ethanol to obtain the desired product (R, R) -bis [1- (2,3,5-triphenylphenyl) -1 -Propyl] disulfide (534 mg, 0.70 mmol, 74% yield) was obtained.

Appearance: White solid
¹ H-NMR (CDCl ₃ ) δ 0.74 (t, 3H, J = 7.6 Hz), 1.75-1.86 (m, 1H), 2.06-2.16 (m, 1H), 3 .67 (dd, 1H, J = 4.8 and 11 Hz), 6.89 (d, 1H, J = 7.6 Hz), 7.03-7.69 (m, 16H).

¹³ C-NMR (CDCl ₃ ) δ 12.2, 27.7, 51.0, 124.6, 126.1, 126.6, 127.1, 127.3127.4, 127.5, 127.8, 128.7, 129.7, 130.4, 130.5, 138.4, 138.7, 140.0, 140.3, 140.5, 141.7, 142.2.

HRMS calcd _{C 54 H 46 S 2 [M} ]: 758.3041, Found: 758.3044.

  Synthesis of ruthenium complex (1) represented by the following formula (12)

[In the above formula, R ₁ S represents a group represented by the following formula (13), and Cp ^* represents η ⁵ -C ₅ Me ₅ (pentamethylcyclopentadiene). ]

Ruthenium complex (Cp ^* RuCl) ₄ (where Cp ^* is the same as above, 65.8 mg, 0.061 mmol), THF (5 ml), and optically active disulfide (S, S) are added to a nitrogen-substituted 20 ml Schlenk tube. -1- (2,3,5-triphenylphenyl) propyl-1-disulfide (91.9 mg, 0.121 mmol) was added, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a black purple solid. As a result of mass spectrometry, a measurement result of 1302 in which one chlorine atom was eliminated from the assumed molecular weight C ₇₄ H ₇₆ Cl ₂ Ru ₂ S ₂ (M / Z = 1302) was obtained.

Reaction of propargyl alcohol and acetone The Schlenk tube containing the ruthenium complex (1) (0.005 mmol) and NH ₄ BF ₃ (0.010 mmol) prepared in Example 3 was purged with nitrogen, and acetone (3 ml) was added and homogeneous. After making into a solution, 1-phenyl-2-propargyl-1-ol (0.100 mmol) was added, and the reaction was carried out under reflux for 6 hours. After completion of the reaction, the solvent was distilled off and the residue was purified by silica gel thin layer chromatography (ethyl acetate / n-hexane = 10/90 vol / vol) to obtain the desired product (0.0066 mmol, yield 66%). The optical selectivity of the obtained product was 69% ee as analyzed by gas chromatography using an optically active column (manufactured by Kadrec, USA, GTA, 30 m).

A reaction was carried out in the same manner as in Example 4 except that NH ₄ BF ₃ (0.010 mmol) was replaced with NH ₄ PF ₆ (0.010 mmol) and acetone (3 ml) was replaced with acetone (1.5 ml). The target product was obtained at a rate of 79% and 69% ee.

Example 6 to Example 10
The reaction was carried out in the same manner as in Example 4 except that 1-phenyl-2-propargyl-1-ol was replaced with the propargyl alcohols shown in Table 1. The results are also shown in Table 1.

Example 11 to Example 15
Catalysts with different R ₃ shown in Table 2 below were prepared according to Examples 1 to 3 and reacted in the same manner as in Example 4 except that the catalysts were changed. The results are also shown in Table 2.

  The novel optically active ruthenium complex of the present invention is a novel catalyst for asymmetric synthesis reaction, and the optically active compound synthesized using the same is useful as a pharmaceutical / pesticidal intermediate and a raw material for electronic materials.

Claims (8)

General formula (1)

[R ₁ S in the above formula represents the general formula (2)

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
And Cp ^* represents η ⁵ -C ₅ Me ₅ (pentamethylcyclopentadiene). ]
An optically active ruthenium complex represented by: In the general formula (1), R ₂ is an ethyl group, R ₃ is a 2-methoxy-5 - phenylphenyl group, 2-methoxy-5- (2-naphthyl) phenyl group, 2- (2-propoxy) -5- Phenylphenyl group, 2,5-diphenylphenyl group, 2,3,5-triphenylphenyl group, 2,3,5- (4-methylphenyl) phenyl group or 2,3,5- (4-tert-butyl) The optically active ruthenium complex represented by the general formula (1) according to claim 1, which is a phenyl) phenyl group. General formula (3)

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
An optically active disulfide compound represented by: In the general formula (3), R ₂ is an ethyl group, R ₃ is a 2-methoxy-5 - phenylphenyl group, 2-methoxy-5- (2-naphthyl) phenyl group, 2- (2-propoxy) -5- Phenylphenyl group, 2,5-diphenylphenyl group, 2,3,5-triphenylphenyl group, 2,3,5- (4-methylphenyl) phenyl group or 2,3,5- (4-tert-butyl) The optically active disulfide compound represented by the general formula (3) according to claim 3, which is a phenyl) phenyl group. Ruthenium complex (Cp ^* RuCl) ₄ [where Cp ^* represents η ⁵ -C ₅ Me ₅ (pentamethylcyclopentadiene). ] And general formula (3)

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
Wherein the disulfide compound represented by the general formula (1) is reacted.

[R ₁ S in the above formula represents the general formula (2)

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
And Cp ^* represents η ⁵ -C ₅ Me ₅ (pentamethylcyclopentadiene). ]
The manufacturing method of the optically active ruthenium complex shown by these. General formula (4)

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
An optically active alcohol represented by the general formula (3) is substituted with an acetylthio group by a steric inversion reaction, then reduced, and then dimerized by oxidation.

(In the above formula, R ₂ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ₃ is a phenyl group in which the nucleus is substituted by 1 to 5 with a phenyl group, or a substituted phenyl group and the nucleus is 1 to 5 A substituted phenyl group, a phenyl group having a nucleus substituted by 1-5 with a naphthyl group, a phenyl group having a nucleus substituted with a naphthyl group by 1-5, a 2-alkoxyphenyl having a nucleus substituted with a phenyl group by 1-4 Group, 2-alkoxyphenyl group whose nucleus is substituted with substituted phenyl group 1-4, 2-alkoxyphenyl group whose nucleus is substituted 1-4 with naphthyl group or substituted naphthyl group with nucleus 1-4 substituted 2 -Represents an alkoxyphenyl group.
The manufacturing method of optically active disulfides shown by these.   A catalyst for an asymmetric synthesis reaction comprising the optically active ruthenium complex according to claim 1. In the presence of the catalyst according to claim 7 , the general formula (6)

(In the above formula, R ₄ is a linear or branched alkyl group having 1 to 10 carbon atoms, phenyl group, 1-naphthyl group, 2-naphthyl group, cycloalkyl group having 3 to 8 carbon atoms, A phenyl group in which the nucleus is substituted with 1 to 5 linear or branched alkyl groups, a phenyl group in which the nucleus is substituted with 1 to 5 linear or branched alkyloxy groups, and a nucleus with halogen 1 to 5 substituted phenyl groups, phenyl groups each substituted 1 to 5 with phenyl groups, 1 to 5 carbon atoms linear or branched alkyl groups with 1 to 5 nucleus substituted 1-naphthyl groups 1-naphthyl group having 1 to 5 carbon atoms substituted with a linear or branched alkyloxy group having 1 to 5 carbon atoms, 1-naphthyl group having 1 to 5 carbon atoms substituted with halogen, 1 to 5 carbon atoms Linear or branched alkyl group with a nucleus of 1 5-substituted 2-naphthyl group, 2-naphthyl group having 1 to 5 carbon atoms substituted with a linear or branched alkyloxy group having 1 to 5 carbon atoms, or 2-naphthyl having 1 to 5 nucleus atoms substituted with halogen Group.)
And propargyl alcohol represented by the general formula (7)

(Wherein R ₅ and R ₆ are each independently hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkynyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. A linear or branched alkenyl group, a phenyl group, a benzyl group, a 1-naphthyl group, a 2-naphthyl group, a phenyl group in which the nucleus is substituted with a linear or branched alkyl group having 1 to 5 carbon atoms, A phenyl group in which the nucleus is substituted by 1 to 5 carbon atoms with a linear or branched alkoxy group having 1 to 5 carbon atoms, a phenyl group in which the nucleus is substituted by 1 to 5 carbon atoms with a halogen atom, a linear or branched chain having 1 to 5 carbon atoms 1-naphthyl group having 1-5 substituted nucleus with alkyl group, 1-naphthyl group having 1-5 substituted nucleus with straight chain or branched alkoxy group having 1-5 carbon atoms, 1-naphthyl group having 1 atom substituted with halogen atom 5-substituted 1-naphthyl group, carbon A 2-naphthyl group in which the nucleus is substituted with 1 to 5 with a linear or branched alkyl group of 1 to 5, or a 2-naphthyl group with a nucleus of 1 to 5 with a linear or branched alkoxy group having 1 to 5 carbon atoms A 2-naphthyl group having a nucleus or a halogen atom substituted with 1 to 5 nuclei.)
Wherein the ketone represented by the general formula (8) is reacted

(Wherein R ₄ , R ₅ and R ₆ have the same definition as above, and * represents an asymmetric carbon.)
The manufacturing method of the ketone derivative shown by these.