Chemistry of Sulfenic Acids. 1. Synthesis of Trimethylsilyl Arenesulfenates (Arenesulfenic Acids)

Article abstract of DOI:10.1021/jo01297a023

Trimethylsilyl arenesulfenates (5), masked sulfenic acids, are prepared in low yield by trapping the intermediate arenesulfenic acid generated by thermolysis of the corresponding N-benzylidenarenesulfinamide (4) with chlorotrimethylsilane-hexamethyldisilazane.Attempts to prepare 5 by oxidation of trialkyl(phenylthio)silanes (8) with 2-(benzenesulfonyl)-3-phenyloxaziridine (11), an aprotic oxidizing reagent, gave instead the previously unknown trialkylsilyl benzenesulfinates (12).These results are attributed to the enhabced nucleophilicity (α effect) of the intermediate trialkylsilyl arenesulfenate ester.