Two efficient procedures involving tin hydride or thiophenol-mediated intramolecular homolytic substitution at the sulfur atom are reported. They lead to the generation of varied P (V)-centered radicals from the corresponding aryl or alkyne thiophosphorus substrates. The radical formed can be trapped by an olefin via an intermolecular addition, leading to the construction of C–P bonds. Thiophosphination of triple bonds was also achieved using a ...
