Enantioselective reductive allylic alkylation enabled by dual photoredox/palladium catalysis.

A dual photoredox/palladium catalyzed regio- and enantioselective reductive cross-coupling of allylic acetates with tertiary/secondary alkyl bromides has been achieved, and Hantzsch ester is used as a homogeneous organic reductant. This straightforward protocol enables the stereoselective construction of C(sp 3 )-C(sp 3 ) bonds under mild reaction conditions. Mechanistic studies suggest that this reaction involves radical pathways and a chiral Pd complex enables the control of the regio- and enantioselectivities.