Ni-Catalyzed Asymmetric Reductive Arylation and Alkenylation of N -Sulfonyl Imines

Chiral α-branched amines represent privileged structural motifs in pharmaceuticals, natural products, and chiral ligands. However, their enantioselective synthesis directly from readily available aryl/alkenyl halides remains a challenge. Herein we report a Ni-catalyzed asymmetric reductive coupling of diverse N -sulfonyl imines with aryl/alkenyl halides. Enabled by a modified chiral biimidazole ligand in conjunction with a cobalt phthalocyanine (CoPc) cocatalyst, this transformation achieves high enantioselectivity under remarkably mild conditions. Demonstrating exceptional generality (>85 substrates), the protocol enables the direct late-stage functionalization of complex drug-derived scaffolds (e.g., naproxen, ibuprofen, oxaprozin, gemfibrozil). The synthetic utility is further highlighted through chemoselective derivatizations. DFT calculations support a mechanism involving Ni I -mediated oxidative cyclometalation proceeding via a key aza-nickelacycle intermediate.