Mn(III)-Catalyzed Synthesis of Selenophosphates and Tellurophosphates

Selenophosphates and tellurophosphates are important classes of organophosphorus compounds that exhibit unique reactivity, tunable redox properties, and significant biological activity. Herein, we report a mild and efficient Mn(III)-catalyzed method for synthesizing selenophosphates and tellurophosphates. Using Mn(OAc)₃ as the catalyst and tetrahydrofuran (THF) as the solvent, various H-phosphonates and H-phosphine oxides undergo radical coupling with diselenides or ditellurides at room temperature in the presence of air, affording good-to-excellent yields of the corresponding chalcogenophosphates. The protocol features a broad substrate scope, favorable functional group tolerance, and low catalyst loading while avoiding the use of toxic reagents or strong oxidants. Mechanistic studies suggest that the reaction proceeds via the phosphinyl radicals generated through single-electron oxidation mediated by Mn(III).