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.