Ligand-Controlled NiH-Catalyzed Regiodivergent Chain-Walking Hydroalkylation of Alkenes.

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.