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.