Diastereo- and enantioselective direct catalytic aldol reaction of 2-hydroxyacetophenones with aldehydes promoted by a heteropolymetallic complex: catalytic asymmetric synthesis of anti-1,2-diols

Naoki Yoshikawa; Takeyuki Suzuki; Masakatsu Shibasaki

doi:10.1021/jo0162538

Diastereo- and enantioselective direct catalytic aldol reaction of 2-hydroxyacetophenones with aldehydes promoted by a heteropolymetallic complex: catalytic asymmetric synthesis of anti-1,2-diols

J Org Chem. 2002 Apr 19;67(8):2556-65. doi: 10.1021/jo0162538.

Authors

Naoki Yoshikawa¹, Takeyuki Suzuki, Masakatsu Shibasaki

Affiliation

¹ Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.

PMID: 11950301
DOI: 10.1021/jo0162538

Abstract

An anti-selective direct catalytic asymmetric aldol reaction of 2-hydroxyacetophenones with aldehydes is described. The reaction is catalyzed by a heteropolymetallic complex to afford anti-alpha,beta-dihydroxy ketones as the major diastereomer with excellent enantioselectivity. The use of 2-hydroxyacetophenones bearing electron-donating groups at the phenyl moiety enabled efficient transformation of the aldol products (alpha,beta-dihydroxy ketones) into the corresponding alpha,beta-dihydroxy ester derivatives via Baeyer-Villiger oxidation. A plausible reaction mechanism is also discussed based on the stereochemistry of the products.