Ligand-Controlled NiH-Catalyzed Regiodivergent and Enantioselective Hydroamination of Alkenyl Amides

Abstract

Transition-metal-catalyzed remote hydrofunctionalization of alkenes remains an efficient but challenging protocol in chemical synthesis. Herein, we reported a ligand-controlled, directing-group-assisted strategy to promote NiH-catalyzed site-selective (α, β, or γ) hydroamination of unactivated alkenes with weakly coordinating amide groups. The key to success lies in the employment of proper yet commercially available bidentate nitrogen-containing ligands, which enables delivery of 1,1-, 1,2-, and 1,3-diamines with good-to-excellent regioselectivity starting from the same substrates. A broad range of O-benzoylhydroxylamine electrophiles with different functional groups can be installed via Ni migration or nonmigration. Moreover, these predicable and positionally selective protocols provide a method for the enantioselective synthesis of highly valued 1,2-diamines (via remote aliphatic C–H amination) and 1,3-diamines.