Manganese Promoted Reductive Cross-Coupling of Phosphine Chlorides with Disulfides for the Synthesis of Thiophosphanes

Herein we reported a manganese promoted reductive cross-coupling approach to construct P‒S bond. This is a practical method for the synthesis of mono-thiophosphanes, bis-thiophosphanes and tri-thiophosphanes under mild conditions. The strategy featured a wide range of substrate scope including various disulfides and phosphine chlorides, constructing diverse sulfur-containing organophosphorus compounds from inodorous and readily available starting materials. The employment of reductive conditions avoided the generation of phosphorothioates (PV) by-products. Ultimately, gram-scale synthesis and applications were explored. Extensive experiments indicated that the phosphine radical cascade process was involved in the catalytic cycle.