A New Reaction of 2-(Phenylsulfonyl)-3-phenyloxaziridine (Davis Reagent): Oxidation of Thiolates to Sulfinates. Application to the Synthesis of Sulfones
Franck Sandrinelli, Stéphane Perrio* and Pierre Beslin
*Laboratoire de Chimie Moléculaire et Thio-organique (Associé au CNRS, UMR 6507), ISMRA-Université de Caen, 6 boulevard du Maréchal Juin, F-14050 Caen, France,
Email: stephane.perrioensicaen.fr
F. Sandrinelli, S. Perrio, P. Beslin, Org. Lett., 1999, 1, 1107-1109.
DOI: 10.1021/ol990170k
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Abstract
2-(Phenylsulfonyl)-3-phenyloxaziridine, commonly known as the Davis reagent, enables a generation of sulfinate anions by oxidation of the corresponding thiolates. Subsequent S-alkylation of the sulfinates under phase-transfer catalysis affords sulfones in very good isolated yields.
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Details
The document describes a novel and efficient method for generating sulfinate anions by oxidizing thiolates using 2-(phenylsulfonyl)-3-phenyloxaziridine, known as the Davis reagent. This method allows for the subsequent S-alkylation of sulfinates under phase-transfer catalysis to produce sulfones in high yields (71-91%). The process involves the oxidation of aromatic thiolates to sulfinates, followed by alkylation to form sulfones. The study highlights the rapidity and efficiency of the double oxidation reaction, which occurs almost immediately at low temperatures. The method is compatible with various substrates and demonstrates high chemoselectivity, making it a promising approach for synthesizing sulfones. The lithium sulfinates formed can also serve as precursors for sulfonyl chlorides or sulfonamides. The research extends the synthetic utility of oxaziridines and suggests that slight modifications in oxaziridine structure can significantly alter reactivity. Future work aims to explore the origin of these differences and apply the method to synthesize 11C-labeled sulfones for biological studies using positron emission tomography. The study was supported by the French Ministry of Education and Research, with additional technical contributions from the University of Würzburg.
Key Words
Davis reagent, alkyl sulfones, oxidation
ID: J54-Y1999