Harnessing gem-Diboron Radicals: A Ni-Catalyzed Reductive Coupling Platform for Diverse sp3-Rich Molecular Architectures.

Herein, we report a practical nickel-catalyzed reductive cross-coupling of α-chloro-gem-diboron compounds with carbon electrophiles, providing efficient access to a broad range of gem-diboron structures, including previously underdeveloped α-arylated derivatives. This transformation proceeds via an underdeveloped gem-diboron radical intermediate pathway and features mild conditions, operational simplicity, excellent regioselectivity, and broad functional group tolerance. Notably, this method overcomes the long-standing challenge of Csp3-Csp3 bond formation using simple alkyl halide electrophiles, thereby expanding access to traditionally elusive molecular scaffolds.