Stereoselective radical additions of γ-oxy-α,β-unsaturated ester derivatives; 1,2-asymmetric induction in acyclic and cyclisation systems

Abstract

Examination was made of 1,2-asymmetric induction in the addition of alkyl radicals to γ-oxy-α,β-unsaturated ester derivatives 1 and 2 prepared from ethyl lactate and (R)-2,3-O-isopropylideneglyceraldehyde 3, respectively. The addition reactions of hexyl, cyclohexyl and 3-phenylpropyl radicals to (Z)-2 derived from aldehyde 3 gave β-addition products with syn-stereoselectivity (syn : anti= 8.6 : 1—syn only). The reactions of (E)-2 where non-stereoselective. Based on allylic strain, a transition-state model for the syn-stereoselectivity is proposed. 1,2-Asymmetric induction was carried out in radical cyclisation to synthesize active cyclohexane derivatives.