Asymmetric paired oxidative and reductive catalysis enables enantioselective alkylarylation of olefins with C(sp)-H bonds.

Enantioselective transformations of hydrocarbons to three-dimensional chiral molecules remain a significant challenge in synthetic chemistry. This study uses asymmetric paired oxidative and reductive catalysis to promote the enantioselective alkylarylation of olefins through the functionalization of C(sp)-H bonds in alkanes. This asymmetric photoelectrocatalytic approach enables the facile construction of a wide range of enantioenriched α-aryl carbonyls with excellent enantioselectivity (up to 96% ee) from readily accessible starting materials. Notably, aryl bromides, aryl iodides, and even aryl chlorides were compatible with the developed catalytic system. Mechanistic studies reveal that alkanes and electrophiles are simultaneously activated on the electrodes.