Synthesis of Organothiophosphates from Sodium Sulfinates and Chlorophosphines via P(III) to P(V) Rearrangement

An efficient synthesis of organothiophosphates from sodium sulfinates and chlorophosphines (R₂PCl) is described. The mechanism involves a P(III) to P(V) rearrangement of S-O-PR₂ species leading to S-P bond formation, which may be catalyzed by chloride ions generated in situ. Notably, the chlorophosphines play dual roles as both the phosphorus source and the reductant. The synthesis features mild conditions, short time, a broad substrate scope, and the use of a stable and odorless sulfur source.