Nickel-Catalyzed Reductive Alkylation of Heteroaryl Imines

A Ni-catalyzed reductive cross-coupling of heteroaryl imines with C(sp3) electrophiles for the preparation of heterobenzylic amines is reported. This umpolung-type alkylation proceeds under mild conditions, avoids the pre-generation of organometallic reagents, and ex-hibits good functional group tolerance. Mechanistic studies are consistent with the imine substrate acting as a redox-active ligand upon coordination to a low-valent nickel center. The resulting Ni-bis(2-imino)heterocycle complexes can engage in alkylation reactions with a variety of C(sp3) electrophiles, giving the heterobenzylic amine products in good yields.