Method of producing optically-active aldehyde

Patent metadata

Field	Value
Publication number	US-10029969-B2
Application number	US-201414767744-A
Country	US
Kind code	B2
Filing date	Mar 6, 2014
Priority date	Mar 6, 2013
Publication date	Jul 24, 2018
Grant date	Jul 24, 2018

Abstract

A method for producing, in a few simple steps, a specific optically active aldehyde represented by the general formula (1), in which * is an asymmetric carbon atom, includes asymmetrically isomerizing a specific allyl alcohol represented by the general formula (2) in the presence of a ruthenium complex and a base.

First claim

The invention claimed is:

1. A method for producing an optically active aldehyde of the formula (1):

wherein R 1 and R 2 are each independently selected from the group consisting of an alkyl group having from 1 to 20 carbon atoms, which may have a substituent, an alkenyl group having from 2 to 20 carbon atoms, which may have a substituent, a 3- to 8-membered alicyclic group which may have a substituent, an aryl group having from 6 to 15 carbon atoms, which may have a substituent, and an aralkyl group having from 7 to 12 carbon atoms, which may have a substituent; R 1 and R 2 are groups different from each other; and * is an asymmetric carbon atom,
the method comprising asymmetrically isomerizing an allyl alcohol of by the formula (2) in the presence of a ruthenium complex and a base in an ethanol solvent:

wherein R 1 and R 2 have the same meanings as described above,
wherein the asymmetric isomerization is carried out using a ruthenium complex of the following general formula (3):
[Ru m L n W p U q ] r Z s   (3)

wherein
(a): L is an optically active bidentate phosphine ligand; W is a chlorine atom, a bromine atom or an iodine atom, Z is dimethylformamide or dimethylacetamide, m=n=r=1, p=2, q=0, and s is an integer of from 0 to 4;
(b): L is an optically active bidentate phosphine ligand; W is a chlorine atom, a bromine atom or an iodine atom, U is a chlorine atom, a bromine atom or an iodine atom, Z is a dialkylammonium ion, m=n=p=2, q=3, r=s=1; or
(c): L is an optically active bidentate phosphine ligand: W and U may be the same or different, representing a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a carboxyl group or any other anion group, Z is a diamine compound, m=n=p=q=r=s=1.

2. The method according to claim 1 , wherein the reaction temperature is 0 to 70° C.

3. The method according to claim 1 wherein the reaction temperature is 0 to 25° C.

Assignees

• Takasago Perfumery Co Ltd

Inventors

• Ohkuma Takeshi
• Arai Noriyoshi
• Matsumura Kazuhiko

Classifications

• C07B2200/07

  Optical isomers · CPC title

• C07C2601/14

  The ring being saturated · CPC title

• C07B53/00 Primary

  Asymmetric syntheses · CPC title

• C07C45/51

  by pyrolysis, rearrangement or decomposition · CPC title

• C07C45/512 Primary

  the singly bound functional group being a free hydroxyl group · CPC title