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Hydroxy-directed iridium-catalyzed enantioselective formal β-C(sp 2 )-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., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The first iridium-catalyzed enantioselective olefinic C(sp 2 )-H allylic alkylation is developed in cooperation with Lewis base catalysis. This reaction, catalyzed by cinchonidine and an in situ generated cyclometalated Ir(i)/phosphoramidite complex, makes use of the latent enolate character of an α,β-unsaturated carbonyl compound, namely coumalate ester, to introduce an allyl group at its α-position in a branched-selective manner in moderate to good yield with good to excellent enantioselectivities (up to 98 : 2 er)., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)