W(CO)6-Mediated Desulfurdimerization of Dithioketals. Evidence for a Thione Intermediate

Article abstract of DOI:10.1021/jo00293a037

Upon treatment with W(CO)6, dithioketals undergo desulfurdimerization to give the corresponding dimeric olefins in good to excellent yields.The mechanism of this the newly discovered reaction has been investigated.Thioketones have been isolated from the reactions of highly crowded dithioketals.The mechanism for the formation of thioketones has been shown to occur via a new type of radical fragmentation process of dithiolane.Thermolysis of 2,2-dimethylindan-1-yl 2-thiophenoxyethyl sulfide in the presence of tert-butyl adamantane-1-peroxycarboxylate (a typical radical initiator) has been studied for comparison.Thioketones react with W(CO)6, giving dimeric olefins and/or undergoing carbene-like insertion reactions.