Cu(I)-Catalyzed Synthesis of Sulfenamides via Coupling of Carbamothioate/Thiourea Derivatives with Sulfonyl Azides

An efficient one-pot protocol is devised to access a wide range of sulfenamide derivatives through the copper-catalyzed coupling of sulfonyl azides with thioamides. The reaction proceeds via a copper–nitrenoid intermediate derived from sulfonyl azides, enabling chemo- and regioselective construction of the S–N bond through the extrusion of nitrogen as the sole byproduct. Notably, the protocol exhibits broad functional group tolerance and scalability. Scale-up reactions and mechanistic studies further underscore the operational simplicity, mild nature, and synthetic utility of this transformation.