Elemental Sulfur/Selenium-Mediated Metal-Free Phosphinothioation and Phosphinoselenoation of Vinylsulfonium Salts with P–H Bonds

An efficient and facile method has been developed for the construction of novel P-S-C and P-Se-C bonds by facilitating the three-component cross-coupling reaction of P-H bonds with elemental sulfur/selenium and vinylsulfonium salts, utilizing sodium bicarbonate as a base. This approach eliminates the need for the use of toxic and odorous active sulfur/selenium reagents and noble metals, thereby offering a new pathway for synthesizing <i>S</i>-phosphinothioates and <i>Se</i>-phosphinoselenoates via the organic conversion of inorganic sources. The reaction has showcased remarkable versatility in terms of substrate applicability, particularly for organophosphorus compounds containing P-H bonds and vinylsulfonium salt derivatives. The resulting phosphinothioation/phosphinoselenoation products can be obtained with high yield and regioselectivity. Additionally, a plausible reaction mechanism for this transformation has been proposed based on step-by-step control experiments and ³¹P NMR tracking analysis.