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 S-phosphinothioates and Se-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.