Nickel/Photoredox‐Catalyzed Dicarbofunctionalization of Alkenes via Ketone C─C Bond Cleavage: Access to an Enantioselective Variant

ABSTRACT In this study, we disclose a general protocol for the three‐component difunctionalization of alkenes using nickel catalysis and aliphatic carbonyl precursors that are activated by sp 3 C─C bond cleavage. Under visible‐light irradiation, this transformation provides an efficient strategy to install two vicinal carbon─carbon bonds across alkenes from easily accessible precursors. Notably, the alkene difunctionalization was extended to an enantioselective variant, providing streamlined access to complex enantioenriched scaffolds. The reaction exhibits operational simplicity, broad substrate scope, and excellent regioselectivity and chemoselectivity while demonstrating compatibility with bioactive motifs and the ability to expedite the synthesis of pharmaceutically relevant molecules.