Abstract
Herein, we report a straightforward method for efficiently obtaining a diverse range of thiophosphonium salts. This method involves the direct coupling of commercially available thiols and aldehydes with Ph3P 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.