Enantioselective Formal Hydration of α,β-Unsaturated Imides by Al-Catalyzed Conjugate Addition of Oxime Nucleophiles

Abstract
The (salen)Al-catalyzed asymmetric conjugate addition of salicylaldoxime to α,β-unsaturated imides is the key step in an efficient and highly enantioselective two-step formal hydration of these electron-deficient olefins. This reaction constitutes the first example of an enantioselective conjugate addition of an oxygen-centered nucleophile to α,β-unsaturated carboxylic acid derivatives. Application of this method to chiral, nonracemic substrates revealed a high level of catalyst-induced diastereoselectivity, underscoring its potential utility for polyketide natural product synthesis.