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A Bench-Stable Platform [TBA][PS2Cl2] Enables Sequential Assembly of Unsymmetric Tri- and Tetrathiophosphates
Guoqing Sun1, Xingwei Xun1, Sitong Zhang1
1Gansu International Scientific and Technological Cooperation Base of Water-Retention Chemical Functional Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu730070, P. R. China.
Abstract:
Unsymmetric tri- and tetrathiophosphates with distinct S-substituents are synthetically challenging. Here, we report a bench-stable P(V)-S platform, tetrabutylammonium dichlorodithiophosphorane ([TBA][PS2Cl2]), prepared by mild redox-neutral halogenation of commercial P4S10 at room temperature. This modular platform enables the selective phosphorothiolation of various thiols, thiophenols, amino acids, short peptides, glycosides, and natural products to construct a broad range of unsymmetric tri- and tetrathiophosphates, which are difficult to synthesize by traditional multistep routes. The products are versatile intermediates for C(sp3)-S, C(sp2)-S, and N-S bond formations, offering a practical toolkit for complex thiophosphate architectures.
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