Hydropersulfide-Mediated Stereoselective and Regioselective Hydrothiolation of P-alkynes

A stereoselective and regioselective hydrothiolation of P-alkynes using hydropersulfides has been developed to synthesize vinyl β-thiophosphonates with exclusive E stereoselectivity without transition-metal catalysts or additives. This protocol tolerates a broad substrate scope including both alkyl and aryl hydropersulfides. Mechanistic investigations indicate that the reaction follows an ionic pathway supported by DFT calculations and NOESY analysis. This method provides a green and general protocol toward vinyl β-thiophosphonates with potential applications in organometallic, medicinal, agricultural, and materials sciences.