From Thiiranes to ThiocarbonylS-Sulfides; Recent Results

Publisher Website
Google Scholar
Abstract
A novel nucleophilic catalysis for the desulfurization of thiiranes is described. Triphenyl-thiirane is quantitatively converted to triphenyl-ethylene by some mol% sodium thiophenoxide or other thiolates in DMSO at 35°C. A rapid initial reaction is retarded by the eliminated sulfur leading to a pseudo-first-order reaction under quasi-stationary conditions. The suggested mechanism is based on structure-rate relationships. - The thiolate-catalyzed reaction of cis-2,3-diphenylthiirane is exceptional in furnishing equimolar quantities of cis-stilbene and 3,4,6,7-tetraphenyl-1,2,5-trithiepane (2 diastereoisomers with bilateral symmetry); mechanistic implications - thiolate attack on sulfur or C-atom of thiirane - are discussed. - Desulfurization of 2,2-diphenylthiirane by thiobenzophenone or other thioketones gives access to thiocarbonyl S-sulfides (“thiosulfines”) which are intercepted by 1,3-cycloadditions to activated acetylenes or to thiones.

This publication has 19 references indexed in Scilit: