title: The Reactions of O(2) ((1)Delta(g)) with Anancomeric 1,3-Dithianes. The First Experimental Evidence in Support of a Hydroperoxy Sulfonium Ylide as a Precursor to Sulfoxide on the Sulfide Singlet Oxygen Reaction Surface.
abstract: The kinetic isotope effects for the formation of anancomeric 1,3-dithiane-1-oxides in the reactions of singlet oxygen with the parent 1,3-dithianes have been determined for a series of 2-protio and 2-deuterio analogues. The substantial isotope effects are used to argue for formation of a hydroperoxysulfonium ylide as a key intermediate in sulfoxide formation. These results confirm an earlier theoretical prediction and force a change in the currently accepted mechanism for this important reaction. The first experimental demonstration of a novel singlet oxygen-induced epimerization of a 1,3-dithiane and a novel intramolecular electron transfer within a hydroperoxysulfonium ylide are also reported.
authors.affiliation: Department of Chemistry, University of Wyoming, Laramie, Wyoming 82071.
authors.forename: A.
authors.initials: A
authors.lastname: Toutchkine
authors.forename: E. L.
authors.initials: EL
authors.lastname: Clennan