Copper-Catalyzed Intermolecular Reductive Radical Difluoroalkylation–Thiolation of Aryl Alkenes

A novel radical-involved alkene difunctionalization catalyzed by the copper/B<sub>2</sub>pin<sub>2</sub> system has been developed, leading to the difluoroalkylation–thiolation of aryl alkenes. The use of B<sub>2</sub>pin<sub>2</sub> as an organic reductant enables the simultaneous installation of a C­(sp<sup>3</sup>)–C­(F<sub>2</sub>R) bond and a C­(sp<sup>3</sup>)–S­(R) bond across the CC bond of aryl alkenes by utilizing two electrophilic reactants. The reaction exhibits broad substrate scope, excellent diastereoselectivity, and moderate to good yields. Moreover, the reaction can be conducted on a gram scale with good yield achieved.