Synthesis of Tetrathiophosphates from White Phosphorus

Comprehensive Summary A transition‐metal‐free one‐pot direct synthesis of tetrathiophosphates (R 1 S) 2 P(S)SR 2 from white phosphorus (P 4 ), through intermediate sodium alkyltetrathiophosphates (R 1 S) 2 P(S)SNa, is presented. In the presence of NaSH, various disulfides such as diaryl disulfidbges and dialkyl disulfides are easily coupled with P 4 to give sodium alkyltetrathiophosphates (R 1 S) 2 P(S)SNa in almost quantitative yield, which react with alkyl halides in one pot to generate (R 1 S) 2 P(S)SR 2 . Furthermore, S ‐(2‐cyanoethyl)‐substituted tetrathiophosphates (R 1 S) 2 P(S)SCH 2 CH 2 CN are successfully designed as a kind of tetrathiophosphorylation reagent to react with diaryl iodonium salts involving deprotection‐dealkylation process.