Dual Nickel- and Photoredox-Catalyzed Asymmetric Reductive Cross-Coupling To Access Chiral Secondary Benzylic Alcohols.

Transition-metal-catalyzed asymmetric cross-coupling represents a powerful strategy for C-C bond formation and the synthesis of enantiomerically pure molecules. Here, we report a dual nickel/photoredox-catalyzed enantioselective reductive cross-coupling of aryl halides with α-bromobenzoates, readily generated from aliphatic aldehydes, to provide diverse chiral secondary benzylic alcohols that are important motifs in bioactive natural products and pharmaceuticals. This dual catalytic system features mild conditions, good functional group tolerance, broad substrate scope, excellent enantiocontrol, and avoidance of stoichiometric metal reductants, presenting great potential for late-stage functionalization of complex molecules.