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DOI: 10.1055/a-1983-1640
Catalyst-Free Synthesis of Phosphorothioates via P–S Coupling Reaction of Dialkyl Phosphites with Thiols
Authors
The authors gratefully acknowledge support by the Institute for Advanced Studies in Basic Sciences (IASBS), Iran.
Abstract
A catalyst-free synthesis of phosphorothioates via a P–S cross-coupling reaction of thiols with dialkyl phosphites has been studied. With presented method, various phosphorothioates were obtained by the reaction of thiols with H-dialkyl phosphites in the presence of DMSO as both solvent and oxidant under transition-metal-free conditions. Mechanistic studies showed that the reaction proceeds with formation of a known disulfide intermediate via the oxidation of thiols in the presence of DMSO. Nucleophilic substitution of dialkyl phosphite with the disulfide intermediate gave phosphorothioate. The presented method is a convenient process for the synthesis of phosphorothioates under catalyst-free conditions.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1983-1640.
Included are spectroscopic characterization data and copies of 1H and 13C NMR for
compounds 3a–p and 4.
- Supporting Information (PDF)
Publikationsverlauf
Eingereicht: 09. Oktober 2022
Angenommen nach Revision: 20. November 2022
Accepted Manuscript online:
20. November 2022
Artikel online veröffentlicht:
13. Dezember 2022
© 2022. Thieme. All rights reserved
Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany
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- 39 Synthesis of Phosphorothioates 3; General Procedure: Thiol (1 mmol) was added to a solution of dialkyl phosphite (2 mmol) in DMSO (2 mL). The reaction mixture was stirred for 12–24 h (Table 2) at 90 °C. EtOAc (20 mL) was added to the reaction mixture and the mixture was washed with NaOH (5%, 10 mL) and brine (10 mL). The organic phase was evaporated, and the pure product was obtained by flash on silica gel with n-hexane–EtOAc (9:1 to 6:4). All products gave satisfactory spectral data in accord with the assigned structures and literature reports (see the Supporting Information).