Copper-Catalyzed Vinylsulfonium Salt Diversification with P(O)–OH Bonds: Phosphoryloxylation via an Ionic Ring-Opening Process

A facile and convenient copper-catalyzed method for constructing C–O–P(O) bonds using vinylsulfonium salts and P(O)–OH nucleophiles has been reported. Within this reaction system, vinylsulfonium salts bearing various substituents and P(O)–OH nucleophiles have demonstrated exceptional substrate compatibility, allowing for the synthesis of the desired products with yields ranging from good to excellent. Notably, this method also facilitates the effective multifunctional reactions of phenylphosphinic acid and inorganic phosphoric acid, thereby offering a novel avenue for the value-added conversion of inorganic phosphorus and underutilized phosphorus resources. Optimized reaction conditions have enabled the facile scale-up of the model reaction to gram-scale experiments, underscoring the system’s robust practicality. Furthermore, through meticulous stepwise controlled experiments, we have elucidated the reaction pathway and proposed a plausible mechanism for this transformation.