Enantioselective C(sp ³ )–C(sp ³ ) Cross-Coupling between Oxacycles and Alkylsilyl Peroxides via a Dual Photoredox/Nickel Catalytic System

Enantioselective C(sp3)–H functionalization offers a powerful approach to the streamlined synthesis of high-value chiral molecules. However, achieving the direct catalytic construction of asymmetric C(sp3)–C(sp3) bonds from hydrocarbon substrates without directing groups remains a challenge. Herein, we outline the development of an enantioselective C(sp3)–C(sp3) cross-coupling between oxacycles and alkylsilyl peroxides via a dual photoredox-nickel catalytic system. Unlike other radical precursors, the reactivity of alkylsilyl peroxides can be finely tuned through variation of the silicon substituents. A chiral nickel catalyst promotes enantioselective alkyl–alkyl radical cross-coupling efficiently, affording a series of enantioenriched oxacyclic compounds. A plausible reaction mechanism is proposed based on the experimental observations.