Dipole interaction-controlled stereoselectivity in aldol reaction of alpha-CF3 enolate with fluoral

Yoshimitsu Itoh; Masahiro Yamanaka; Koichi Mikami

doi:10.1021/ol0358307

Dipole interaction-controlled stereoselectivity in aldol reaction of alpha-CF3 enolate with fluoral

Org Lett. 2003 Dec 11;5(25):4807-9. doi: 10.1021/ol0358307.

Authors

Yoshimitsu Itoh¹, Masahiro Yamanaka, Koichi Mikami

Affiliation

¹ Department of Applied Chemistry, Tokyo Institute of Technology, Tokyo 152-8552, Japan.

PMID: 14653679
DOI: 10.1021/ol0358307

Abstract

The stereoselectivity of a reaction is generally determined by minimizing steric repulsion. However, the aldol reaction of alpha-CF(3)-ketone (Z)-enolate with fluoral anomalously gave an anti-aldol through a sterically demanding transition state, because of the strong dipole interaction of the two CF(3) groups. We have thus disclosed a paradigm shift from steric to electronic control of reaction stereoselectivity. [reaction: see text]