Hydroxy-directed iridium-catalyzed enantioselective formal β-C(sp2)–H allylic alkylation of α,β-unsaturated carbonyls

Abstract

Hydroxy-directed iridium-catalyzed enantioselective formal β-C(sp²)–H allylic alkylation of kojic acid and structurally related α,β-unsaturated carbonyl compounds is developed. This reaction, catalyzed by an Ir(I)/(P,olefin) complex, utilizes the nucleophilic character of α-hydroxy α,β-unsaturated carbonyls, to introduce an allyl group at its β-position in a branched-selective manner in good to excellent yield with uniformly high enantioselectivity (up to >99.9 : 0.1 er). To the best of our knowledge, this report represents the first example of the use of kojic acid in a transition metal catalyzed highly enantioselective transformation.