Enantioselective α-Allylation of Anilines Enabled by a Combined Palladium and Photoredox Catalytic System

An enantioselective and branch-regioselective alpha-allylation of N-methyl anilines under dual palladium/photoredox catalysis is described. Readily available N-methyl anilines are used as formal hard alkyl nucleophiles without preactivation. Acetic acid is the only side product, which leads to a high atom economy of this reaction. This protocol shows good functional group tolerance and broad scope. A range of chiral homoallylic amines were prepared in moderate to good yields (up to 76%) and excellent regioselectivities (B:L > 95:5 in all cases) and enantioselectivities (up to 96% ee) under mild reaction conditions.