Regio- and Enantioselective Nickel-Catalyzed Hydroamination of Unactivated Alkenes with Anthranils

Anthranils serve as versatile electrophilic amination agents for diverse C–N bond formations, yet achieving regioselective and enantioselective hydroamination of unactivated alkenes has remained a significant challenge. Herein, we report a NiH-catalyzed highly regio- and enantioselective hydroamination of unactivated alkenes with anthranils, providing a wide range of chiral amines bearing various functional groups and heterocyclic scaffolds in good yields with high enantioselectivities (72 examples, up to 97% yield and 99% ee). Both terminal and internal unactivated alkenes are compatible with this reaction, and good functional tolerance and mild conditions allow a late-stage hydroamination reaction of various biologically active molecule-derivatized alkenes and anthranils. Mechanistic studies support that the reaction proceeds via nickel-nitrenoid transfer.