Abstract
Comprehensive SummaryA transition‐metal‐free one‐pot direct synthesis of tetrathiophosphates (R1S)2P(S)SR2 from white phosphorus (P4), through intermediate sodium alkyltetrathiophosphates (R1S)2P(S)SNa, is presented. In the presence of NaSH, various disulfides such as diaryl disulfidbges and dialkyl disulfides are easily coupled with P4 to give sodium alkyltetrathiophosphates (R1S)2P(S)SNa in almost quantitative yield, which react with alkyl halides in one pot to generate (R1S)2P(S)SR2. Furthermore, S‐(2‐cyanoethyl)‐substituted tetrathiophosphates (R1S)2P(S)SCH2CH2CN are successfully designed as a kind of tetrathiophosphorylation reagent to react with diaryl iodonium salts involving deprotection‐dealkylation process.
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