Rhodium-Catalyzed Branched and Enantioselective Direct α-Allylic Alkylation of Simple Ketones with Alkynes.

Herein, we report the first direct branched-selective α-allylic alkylation of simple ketones with alkynes under rhodium and secondary amine cooperative catalysis. Through a rhodium-hydride-catalyzed allylic substitution pathway, a series of valuable γ,δ-unsaturated ketones are obtained with excellent regioselectivity in an atom-economic and byproduct-free manner. With a chiral BIPHEP ligand, high enantioselectivity has been achieved for this transformation.