Synthesis and Functionalization of Thiophosphonium Salts: A Divergent Approach to Access Thioether, Thioester, and Dithioester Derivatives

[Image: see text] Herein, we report a straightforward practical method for efficiently obtaining a diverse range of thiophosphonium salts. This method involves the direct coupling of commercially available thiols and aldehydes with Ph(3)P and TfOH. The setup is simple and carried out in a metal-free manner. The synthetic utility of these salts is demonstrated through various examples of C–P bond functionalizations, enabling the synthesis of thioether, deuterated thioether, thioester, and dithioester derivatives. These products, which serve as valuable building blocks, are obtained in high yields.