Catalytic C-S bond cleavage of simple sulfides with productive retention of thiol fragments.

A mild catalytic strategy for sulfur-retentive C-S bond cleavage of simple sulfides has been developed through cooperative zirconocene and photoredox catalysis. In contrast to conventional desulfurization and radical-generation strategies, which were primarily designed to exploit the carbon fragment upon C-S bond cleavage, this method converts structurally simple sulfides into carbon-centered radicals and isolable or synthetically usable thiols under mild conditions. The transformation is driven by the formation of a strong Zr-S bond and accommodates a broad range of substrates, including benzyl and allyl sulfides, thioglycolates, thioacetals, and cysteine derivatives. The carbon-centered radicals participate in hydrogenation and intermolecular alkylation reactions, while the thiol fragments are conserved as versatile synthetic handles for subsequent functionalization. This strategy establishes simple sulfides as bifunctional precursors that enable productive utilization of both fragments generated upon C-S bond cleavage.