Abstract
Metallaphotoredox processes have emerged as powerful methods for CÀ C bond formations. The Ni-photoredox catalyzed desulfurative cross-coupling of thiol derivatives with aryl bromides has now been established. This procedure provides access to simple and complex unsymmetrical diarylmethane molecules under mild reaction conditions with a broad functional group tolerance. The key steps of the reaction involve a silane-mediated halogen-atom transfer (XAT) and a subsequent intramolecular homolytic substitution (SH), forming C-centered radicals from various thiol derivatives as shown by mechanistic studies. This study paves the way for new transformations of abundant, naturally occurring thiols.