Photoinduced Nickel‐Catalyzed Carbon–Heteroatom Coupling

Herein, we report visible light‐promoted single nickel catalysis for diverse carbon–heteroatom couplings under mild conditions. This mild, general, and robust method to couple diverse nitrogen, oxygen, and sulfur nucleophiles with aryl(heteroaryl)/alkenyl iodides/bromides exhibits a wide functional group tolerance and is applicable to late‐stage modification of pharmaceuticals and natural products. On the base of preliminary mechanistic studies, a NiI/NiIII cycle via the generation of active NiI complexes that appear from homolysis of NiII−I rather than NiII−aryl bond was tentatively proposed. Exogenous photocatalyst‐free, single nickel‐catalyzed carbon–heteroatom coupling under visible‐light irradiation is reported. Over 15 classes of nucleophile can efficiently couple with aryl/alkene halides to afford valuable heteroatomic arenes/alkenes. The unprecedentedly broad substrate scope and late‐stage modification of valuable molecules fully demonstrate the benefits of the method.