Ligand‐Controlled NiH‐Catalyzed Regiodivergent Chain‐Walking Hydroalkylation of Alkenes

Abstract

Abstract A NiH‐catalyzed migratory hydroalkylation of alkenyl amines with predictable and switchable regioselectivity is reported. By utilizing a ligand‐controlled, directing group‐assisted strategy, various alkyl units are site‐selectively installed at inert sp 3 C−H sites far away from the original C=C bonds. A range of structurally diverse α‐ and β‐branched protected amines are conveniently synthesized via stabilization of 5‐ and 6‐membered nickelacycles respectively. This method exhibits broad scope and high functional group tolerance, and can be applied to late‐stage modification of medicinally relevant molecules.