Photocatalyzed Oxycarboranylation and Hydrocarboranylation of Unsaturated C-C Bonds with 1-Iodo-2-methyl-o-carboranes as the Synthon.

Carboranes, serving as three-dimensional surrogates for benzene and core skeletons of boron neutron capture therapy (BNCT) reagents, have become increasingly vital in medicinal chemistry. Traditional carbon-site functionalization of carboranes relying on strong base-mediated deprotonation inherently restricts reaction diversity. Herein, we report a polarity-matching-driven halogen atom transfer strategy, enabling the generation of open-shell carbon-centered carborane radicals. Regulating redox conditions achieves radical additions to alkynes, alkenes, and benzene, yielding carborane-incorporated ketones, arenes, alkanes, and Z-olefins.