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The oxidation reaction of aliphatic thiocarbonyl compounds has been revisited in order to give access to the elusive corresponding suljines and to achieve thiophilic addition of nucleophiles. Various compounds (thioketones, dithioesters, thionesters, trithiocarbonates, trithioperesters) have been treated with a peroxycarboxylic acid. In all cases the corresponding sulfnes are formed, in contrast to literature expectations. Their behaviour towards nucleophiles has been investigated. The reaction with alkylithiums proved very useful: a clean and rapid thiophilic addition (no enethiolization) was observed at -78 "C. The resulting dithioacetal monoxides are easily transformed into carbonyl compounds (aldehydes, ketones) either by a simple mineral acid treatment or by a spontaneous rearrangement which takes place at ambient temperature. It provides a new formal entry to acyl anions Cformed by an addition reaction and not by deprotonation). A second illustration of the specijic properties of sulfur compounds is disclosed with a new asymmetric version of the Claisen rearrangement. Sulfur is used to facilitate the thermal course of the reaction and a sulfinyl adjacent group is introduced for diastereocontrol First examples show that this transposition indeed occurs at room temperature and with an excellent diastereomeric ratio (2 93:7). Sulfur plays a major role in heteroatom chemistry (1). We wish to report our recent results showing more applications to organic synthesis for the specific properties of some sulfur groups. Replacement of the oxygen of a carbonyl group by a sulfinyl group (using a sulfine) allows to reverse the polarity of the C=S moiety and the attack of a nucleophile takes place on sulfur rather than on carbon. TMoDhiIlc addNon

New developments of thiocarbonyl compounds and sulfines in organic synthesis