Process for producing alcohol analogue

Patent metadata

Field	Value
Publication number	US-10029968-B2
Application number	US-201515514405-A
Country	US
Kind code	B2
Filing date	Aug 31, 2015
Priority date	Sep 26, 2014
Publication date	Jul 24, 2018
Grant date	Jul 24, 2018

Abstract

Provided is a process for producing an optically active hydroxyaldehyde or aminohydroxyaldehyde. The process for producing an optically active hydroxyaldehyde or aminohydroxyaldehyde is characterized by reacting an aldehyde or an imine with a boric acid enol ester in the presence of a copper compound and an optically active bidentate phosphine compound.

First claim

The invention claimed is:

1. A method for producing a compound represented by the following general formula (3):

(wherein, R 1 represents an optionally substituted hydrocarbon group, or an optionally substituted heterocyclic group. R 2 represents a hydrogen atom or a C 1-6 alkyl group. Y represents a hydroxy group or NHX (X represents an optionally substituted thiophosphinoyl group). n represents 0 or 1.
* represents an asymmetric carbon atom.),
characterized in that a borate enol ester represented by the following general formula (2):

(wherein, R 2 represents a hydrogen atom or a C1-6 alkyl group. R 3 and R 4 each represents a C 1-4 alkyl group, or R 3 and R 4 optionally together form a methylene chain which is optionally substituted with alkyl group(s).) is reacted with a compound represented by the following general formula (1):
R 1 CH =Z  (1)

(wherein, R 1 represents an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group. Z represents an oxygen atom or NX (X represents an optionally substituted thiophosphinoyl group.)) in the presence of a copper compound and an optically active bidentate phosphine compound.

2. The method according to claim 1 which further comprises a step of reacting a reaction product produced by the method of claim 1 with a borate enol ester represented by the general formula (2).

3. The method according to claim 1 , wherein the borate enol ester of the general formula (2) is obtained by the isomerization reaction of the following scheme using an iridium catalyst:

(wherein, in the scheme, R 2 represents a hydrogen atom or a C 1-6 alkyl group. R 3 and R 4 each represents a C 1-4 alkyl group, or R 3 and R 4 optionally together form a methylene chain which is optionally substituted with alkyl group(s)).

4. The method according to claim 1 , wherein the optically active bidentate phosphine compound is a phosphine compound represented by the following general formula (4):

(wherein, in the formula (4), R 5 , R 6 , R 7 and R 8 each independently represent a phenyl group, a cyclopentyl group or a cyclohexyl group which is optionally substituted with substituent(s) selected from the group consisting of an alkyl group, an alkoxy group and a halogen atom. R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 may be the same or different from one another, and each represents a hydrogen atom, an optionally substituted alkyl group, an alkoxy group, an acyloxy group, a halogen atom, a haloalkyl group or a dialkylamino group, or R 10 and R 11 , and R 12 and R 13 optionally together form an optionally substituted methylene chain or an optionally substituted alkylenedioxy group, with the proviso that R 11 and R 12 are not a hydrogen atom).

5. The method according to claim 2 , wherein the borate enol ester of the general formula (2) is obtained by the isomerization reaction of the following scheme using an iridium catalyst:

(wherein, in the scheme, R 2 represents a hydrogen atom or a C 1-6 alkyl group. R 3 and R 4 each represents a C 1-4 alkyl group, or R 3 and R 4 optionally together form a methylene chain which is optionally substituted with alkyl group(s)).

6. The method according to claim 2 , wherein the optically active bidentate phosphine compound is a phosphine compound represented by the following general formula (4):

wherein, in the formula (4), R 5 , R 6 , R 7 and R 8 each independently represent a phenyl group, a cyclopentyl group or a cyclohexyl group which is optionally substituted with substituent(s) selected from the group consisting of an alkyl group, an alkoxy group and a halogen atom. R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 may be the same or different from one another, and each represents a hydrogen atom, an optionally substituted alkyl group, an alkoxy group, an acyloxy group, a halogen atom, a haloalkyl group or a dialkylamino group, or R 10 and R 11 , and R 12 and R 13 optionally together form an optionally substituted methylene chain or an optionally substituted alkylenedioxy group, with the proviso that R 11 and R 12 are not a hydrogen atom.

7. The method according to claim 3 , wherein the optically active bidentate phosphine compound is a phosphine compound represented by the following general formula (4):

wherein, in the formula (4), R 5 , R 6 , R 7 and R 8 each independently represent a phenyl group, a cyclopentyl group or a cyclohexyl group which is optionally substituted with substituent(s) selected from the group consisting of an alkyl group, an alkoxy group and a halogen atom. R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 may be the same or different from one another, and each represents a hydrogen atom, an optionally substituted alkyl group, an alkoxy group, an acyloxy group, a halogen atom, a haloalkyl group or a dialkylamino group, or R 10 and R 11 , and R 12 and R 13 optionally together form an optionally substituted methylene chain or an optionally substituted alkylenedioxy group, with the proviso that R 11 and R 12 are not a hydrogen atom.

8. The method according to claim 5 , wherein the optically active bidentate phosphine compound is a phosphine compound represented by the following general formula (4):

wherein, in the formula (4), R 5 , R 6 , R 7 and R 8 each independently represent a phenyl group, a cyclopentyl group or a cyclohexyl group which is optionally substituted with substituent(s) selected from the group consisting of an alkyl group, an alkoxy group and a halogen atom. R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 may be the same or different from one another, and each represents a hydrogen atom, an optionally substituted alkyl group, an alkoxy group, an acyloxy group, a halogen atom, a haloalkyl group or a dialkylamino group, or R 10 and R 11 , and R 12 and R 13 optionally together form an optionally substituted methylene chain or an optionally substituted alkylenedioxy group, with the proviso that R 11 and R 12 are not a hydrogen atom.

Assignees

• Takasago Perfumery Co Ltd

Inventors

• Kanai Motomu
• Matsunaga Shigeki

Classifications

• C07C45/511

  involving transformation of singly bound oxygen functional groups to >C = O groups (involving two hydroxy groups C07C45/52; hydroperoxides C07C45/53) · CPC title

• C07C47/273

  containing halogen · CPC title

• B01J2531/0241

  Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution · CPC title

• B01J2531/0266

  Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL" · CPC title

• C07F9/5027

  Polyphosphines · CPC title