We report a catalytic strategy for generating carbon-centered radicals from organoboron compounds under deep-red to near-infrared (DR to NIR) light irradiation via direct excitation of substrate–catalyst complexes. Aza-dipyrromethene (ADP) catalysts form photoactive borate intermediates that enable C–B bond cleavage through ligand-induced photochemical activation. Mechanistic studies support the role of direct excitation. This method allows diverse transformations, including Giese addition, C–heteroatom bond formation, radical–radical coupling, and nickel-catalyzed cross-coupling reactions.
DOI: 10.1021/jacs.5c17266