# US 2013/0158276 A1 · Ruthenium-diamine complexes and method for producing optically active compounds

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 2013/0158276 A1
- Document ID: US20130158276A1
- Status: Published application
- Kind: A1
- Application number: 13/819,188
- Filed: 2011-06-17
- Published: 2013-06-20
- Earliest claimed: 2010-08-26
- Assignees: Takasago International Corporation
- Inventors: Taichiro Touge; Hideki Nara; Tomohiko Hakamada
- Web page: https://patentgrep.com/patent/US20130158276A1

## CPC

- B01J 31/1805: {the ligands containing nitrogen}
- B01J 31/2295: {Cyclic compounds, e.g. cyclopentadienyls}
- C07C 29/143: of ketones
- C07C 209/52: by reduction of imines or imino-ethers (C07C209/24 takes precedence)
- C07C 253/30: by reactions not involving the formation of cyano groups
- C07D 307/42: Singly bound oxygen atoms
- C07D 311/22: with oxygen or sulfur atoms directly attached in position 4
- C07F 15/0046: {Ruthenium compounds}
- C07F 19/00: Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
- B01J 2231/326: Diels-Alder or other [4+2] cycloadditions, e.g. hetero-analogues
- B01J 2231/643: of R2C=O or R2C=NR (R= C, H)
- B01J 2231/646: of aromatic or heteroaromatic rings
- B01J 2531/0208: Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
- B01J 2531/821: Ruthenium
- B01J 2540/32: Sulfonic acid groups or their salts
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

Provided is a catalyst for asymmetric reduction, which can be produced by a convenient and safe production method, has a strong catalytic activity, and has excellent stereoselectivity. The present invention relates to a ruthenium complex represented by the following formula (1): wherein R1 represents an alkyl group or the like; Y represents a hydrogen atom; X represents a halogen atom or the like; j and k each represent 0 or 1; R2 and R3 each represent an alkyl group or the like; R11 to R19 each represent a hydrogen atom, an alkyl group or the like; Z represents oxygen or sulfur; n1 represents 1 or 2; and n2 represents an integer from 1 to 3, a method for producing the ruthenium complex, a catalyst for asymmetric reduction formed from the ruthenium complex, and methods for selectively producing an optically active alcohol and an optically active amine using the catalyst for asymmetric reduction.

## Claims

### Claim 1

A ruthenium complex represented by the following formula (1):
wherein symbol * represents an asymmetric carbon atom;
R1 represents an alkyl group having 1 to 10 carbon atoms; a halogenated alkyl group having 1 to 10 carbon atoms; 10-camphoryl group; an amino group which may be substituted with one or two alkyl group having 1 to 10 carbon atoms; an aryl group which may be substituted with an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogen atom, a cyano group (—CN), an amino group, an alkylated amino group (—NR20R21), a five or six membered cyclic amino group, an acylated amino group (—NH—CO—R20), a hydroxyl group, an alkoxy group (—OR20), an acyl group (—CO—R20), a carboxyl group, an alkoxycarbonyl group (—COOR20), a phenoxy carbonyl group, a mercapto group, an alkylthio group (—SR20), a silyl group (—SiR20R21R22), or a nitro group (—NO2); R20, R21 and R22 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms;
Y represents a hydrogen atom;
X represents a trifluoromethanesulfonyloxy group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, a benzenesulfonyloxy group, a hydrogen atom, or a halogen atom;
j and k each represent 0 or 1, but j+k is not 1;
R2 and R3 each independently represent a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom; or a cycloalkyl group having 3 to 8 carbon atoms, or R2 and R3 may be joined together to form a ring;
R11, R12, R13, R14 and R15 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms;
R16, R17, R18 and R19 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, or R16 and R17 with the carbon atom which is substituted with R16 and R17, and/or R18 and R19 with the carbon atom which is substituted with R18 and R19 may form a carbonyl group(s);
Z represents an oxygen atom or a sulfur atom; and
n1 represents 1 or 2, and n2 represents an integer from 1 to 3.

### Claim 2

A ruthenium complex represented by the following formula (2):
wherein symbol * represents an asymmetric carbon atom;
R1 represents an alkyl group having 1 to 10 carbon atoms; a halogenated alkyl group having 1 to 10 carbon atoms; 10-camphoryl group; an amino group which may be substituted with one or two alkyl group having 1 to 10 carbon atoms; an aryl group which may be substituted with an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogen atom, a cyano group (—CN), an amino group, an alkylated amino group (—NR20R21), a five or six membered cyclic amino group, an acylated amino group (—NH—CO—R20), a hydroxyl group, an alkoxy group (—OR20), an acyl group (—CO—R20), a carboxyl group, an alkoxycarbonyl group (—COOR20), a phenoxy carbonyl group, a mercapto group, an alkylthio group (—SR20), a silyl group (—SiR20R21R22), or a nitro group (—NO2); R20, R21 and R22 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms;
Y represents a hydrogen atom;
R2 and R3 each independently represent a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom; or a cycloalkyl group having 3 to 8 carbon atoms, or R2 and R3 may be joined together to form a ring;
R11, R12, R13, R14 and R15 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms;
R16, R17, R18 and R19 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, or R16 and R17 with the carbon atom which is substituted with R16 and R17, and/or R18 and R19 with the carbon atom which is substituted with R18 and R19 may form a carbonyl group(s);
Z represents an oxygen atom or a sulfur atom;
Q− represents a counter anion; and
n1 represents 1 or 2, and n2 represents an integer from 1 to 3.

### Claim 3

A ruthenium complex represented by the following formula (3):
wherein symbol * represents an asymmetric carbon atom;
R1 represents an alkyl group having 1 to 10 carbon atoms; a halogenated alkyl group having 1 to 10 carbon atoms; 10-camphoryl group; an amino group which may be substituted with one or two alkyl group having 1 to 10 carbon atoms; an aryl group which may be substituted with an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogen atom, a cyano group (—CN), an amino group, an alkylated amino group (—NR20R21), a five or six membered cyclic amino group, an acylated amino group (—NH—CO—R20), a hydroxyl group, an alkoxy group (—OR20), an acyl group (—CO—R20), a carboxyl group, an alkoxycarbonyl group (—COOR20), a phenoxy carbonyl group, a mercapto group, an alkylthio group (—SR20), a silyl group (—SiR20R21R22), or a nitro group (—NO2); R20, R21 and R22 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms;
Y represents a hydrogen atom;
R2 and R3 each independently represent a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom; or a cycloalkyl group having 3 to 8 carbon atoms, or R2 and R3 may be joined together to form a ring;
R11, R12, R13, R14 and R15 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms;
R16, R17, R18 and R19 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, or R16 and R17 with the carbon atom which is substituted with R16 and R17, and/or R18 and R19 with the carbon atom which is substituted with R18 and R19 may form a carbonyl group(s);
Z represents an oxygen atom or a sulfur atom;
V represents a halogen atom; and
n1 represents 1 or 2, and n2 represents an integer from 1 to 3.

### Claim 4 (depends on 1)

A method for producing a reduction product by reducing an organic compound in the presence of the ruthenium complex as set forth in claim 1 and a hydrogen donor.

### Claim 5 (depends on 1)

A method for producing an optically active alcohol, the method comprising reducing a carbonyl group of a carbonyl compound in the presence of the ruthenium complex according to claim 1 and a hydrogen donor.

### Claim 6 (depends on 1)

A method for producing an optically active amine, the method comprising reducing an imino group of an imine compound in the presence of the ruthenium complex according to claim 1 and a hydrogen donor.

### Claim 7 (depends on 4)

The method according to claim 4, wherein the hydrogen donor is selected from formic acid, a formic acid alkali metal salt, and an alcohol having a hydrogen atom on the α-position carbon atom substituted with a hydroxyl group.

### Claim 8 (depends on 4)

The method according to claim 4, wherein the hydrogen donor is hydrogen.

### Claim 9 (depends on 4)

A catalyst for reduction, comprising the ruthenium complex according to claim 4.

### Claim 10 (depends on 9)

The catalyst according to claim 9, wherein the catalyst is a catalyst for asymmetric reduction.