Abstract
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 exhibits good functional group tolerance. Mechanistic studies are consistent with the imine substrate acting as a redox-active ligand upon coordination to a low-valent Ni center. The resulting bis(2-imino)heterocycle·Ni complexes can engage in alkylation reactions with a variety of C(sp3) electrophiles, giving heterobenzylic amine products in good yields.
Version notes
Updated draft with additional mechanistic experiments and electrochemical scope.
Content

Supplementary material

Supporting Information
Experimental procedures, characterization data, computational details