Generation of phosphorus-centered radicals via homolytic substitution at sulfur

A novel radical domino process relying on the homolytic cleavage of P-S bonds allows the preparation of phosphorus-containing molecules through addition of P-centered radicals onto olefins. The key step of this reaction is a homolytic substitution on a sulfur atom. The scope of the reaction is broad. Diaminophosphonyl radicals whose reactivity was unknown react smoothly with olefins. Use of tin hydride can be avoided. A radical thiophosphinoylation of triple bonds has been uncovered.