Iridium-catalyzed enantioselective olefinic C(sp2)-H allylic alkylation (vol 12, pg 3070, 2021)

The first iridium-catalyzed enantioselective olefinic C(sp2)-H allylic alkylation is developed in cooperation with Lewis base catalysis. This reaction, catalyzed by cinchonidine and anin situgenerated 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). © The Royal Society of Chemistry 2021.