An intermolecular syn-1,2-arylamination of unactivated alkenes with arylboronic acids and O-benzoylhydroxylamine electrophiles has been developed with Ni(II) catalyst. The cleavable bidentate picolinamide directing group facilitated formation of stabilized 4-, 5- or 6-membered nickelacycles and enabled the difunctionalization of diverse alkenyl amines with high levels of regio-, chemo- and diastereocontrol. This general and practical protocol was compatible with broad substrate scope and high functional group tolerance. The utility of this method was further demonstrated by the site-selective late-stage modification of pharmaceutical agents.

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 sp3 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.