Harnessing <i>gem</i>-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-<i>gem</i>-diboron compounds with carbon electrophiles, providing efficient access to a broad range of <i>gem</i>-diboron structures, including previously underdeveloped α-arylated derivatives. This transformation proceeds via an underdeveloped <i>gem</i>-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.