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Abstract
Abstract Direct oxidation of enethiolizable thioketones and dithioesters with a peroxycarboxylic acid affords the corresponding sulfines quantitatively. This observation stands in contrast with literature expectations, stating that this reaction would lead to divin disulfides. The oxidation shows a high stereoselectivity: delivery of the oxygen proceeds from the side opposite to the alkylthio group of dithioesters and from the side opposite to the more hindered substituent in the case of thioketones. The thermal stability of these sulfines was studied and a novel rearrangement was observed. The second part of this report deals with the thio-Claisen rearrangement of precursors bearing a chiral centre adjacent to the pericyclic nucleus and its use for stereocontrol in the acyclic series. This thermally facile transposition leads to allylated dithioesters with good to excellent yields. A high diastereomeric selectivity was obtained in a number of cases involving either a steric effect with alkyl groups on the chiral centre or a noteworthy electronic effect when this centre bears a heteroatomic group. It was also carried out in the homochiral series. A favoured conformation and approach model is proposed to explain the formation of syn isomers.
Published Version
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