Synthesis of Tetrathiophosphates from White Phosphorus

A transition-metal-free one-pot direct synthesis of tetrathiophosphates (R1S)2P(S)SR2 from white phosphorus (P4), through inter-mediate S-sodium S,S-dialkylphosphorotetrathioates (R1S)2P(S)SNa, is presented. In the presence of NaSH, various disulfides such as diaryl disulfides and dialkyl disulfides are easily coupled with P4 to give S-sodium S,S-dialkylphosphorotetrathioates (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 reagents to react with diaryl iodonium salts involving deprotection-dealkylation process. Cite this paper:Chin. J. Chem. 2023 , 41 , XXX—XXX. DOI: 10.1002/cjoc.202300XXX Synthesis of Tetrathiophosphates from White Phosphorus Jiali He, Shanshan Shi, Yumeng Zhang,Yang Zhang, Pengxiang Xu, Guo Tang,* and Yufen Zhao a Department of Chemistry, College of Chemistry and Chemical Engineering, and the Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen, Fujian 361005, China b School of Chemistry and Chemical Engineering, Hefei Normal University, Hefei 230601, China.

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