Synthesis of Tetrathiophosphates from White Phosphorus

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.

Additive-free aerobic oxidative difunctionalization of alkenes with P4S10 and alcohols to access β-hydroxy phosphorodithioates

“…5,6 Thus, some elegant synthetic methods have been exploited to access phosphorodithioates. 7–11 For example, Tang described a chiral (salen)Ti( iv ) promoted enantioselective ring-opening of epoxides with dithiophosphorus acids to synthesize β-hydroxy phosphorodithioates (Scheme 1b). 9 Zhao reported a copper catalyzed synthesis of aryl phosphorothioates via the reactions of arylboronic acids/diazonium salts with S 8 and P(S)H compounds (Scheme 1c).…”

“…10 In 2020, Tang also presented a new method for the synthesis of phosphorothioates by using white phosphorus as a substitute. 11 P 4 S 10 as a commercially available thionation reagent has been increasingly utilized in organic synthesis. 12 Very recently, Zhou and Lu developed a regioselective ring-opening of spirovinylcyclopropyl oxindoles with P 4 S 10 to construct allyl dialkylphosphorodithioates (Scheme 1d).…”