Catalytic asymmetric synthesis of alpha-alkylidene-beta-hydroxy esters via dynamic kinetic asymmetric transformation involving Ba-catalyzed direct aldol reaction

Akitake Yamaguchi; Shigeki Matsunaga; Masakatsu Shibasaki

doi:10.1021/ja904575e

Catalytic asymmetric synthesis of alpha-alkylidene-beta-hydroxy esters via dynamic kinetic asymmetric transformation involving Ba-catalyzed direct aldol reaction

J Am Chem Soc. 2009 Aug 12;131(31):10842-3. doi: 10.1021/ja904575e.

Authors

Akitake Yamaguchi¹, Shigeki Matsunaga, Masakatsu Shibasaki

Affiliation

¹ Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.

PMID: 19722664
DOI: 10.1021/ja904575e

Abstract

A Ba-catalyzed dynamic kinetic asymmetric transformation (DYKAT) involving a direct aldol/retro-aldol reaction of beta,gamma-unsaturated ester donors is described. A Ba(O-iPr)(2)/BINOL complex promoted the direct aldol reaction/isomerization sequence, and alpha-alkylidene-beta-hydroxy esters were obtained from aryl, heteroaryl, alkenyl, and alkyl aldehydes under simple proton-transfer conditions with 99-87% ee and >20:1 to 15:1 alpha/gamma selectivity.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Aldehydes / chemistry*
Barium / chemistry*
Catalysis
Esters / chemical synthesis*
Isomerism
Kinetics

Substances

Aldehydes
Esters
Barium
3-hydroxybutanal