Decavanadate‐Catalyzed Oxidative Cross‐Dehydrogenative Coupling: An Efficient and Sustainable Approach towards P(O)−S Bond Formation

A convenient green protocol has been developed for the cross‐dehydrogenative coupling between thiols and P(O)−H compounds using decavanadate anion as the catalyst at room temperature under open‐flask conditions. The reaction proceeds efficiently in water or ethanol without any assistance of heat, light, electricity, or unfriendly additives and tolerates a broad spectrum of functional groups, delivering the desired products in up to 95% yield. Importantly, the decavanadate catalyst can be easily recycled in gram‐scale synthesis at least six times without a significant decline in reaction yield. Further mechanistic investigations evidence the formation of quadrivalent vanadium‐hydroxo‐species in the reaction process and reveal that the P(O)−S dehydrogenative coupling is enabled via a VV to VIV catalytic cycle.