Sulfonyl esters 3. The formation of sulfone-sulfonates in the reactions of aryl methanesulfonates with sodium hydride

Abstract

Sodium hydride reductions of aryl methanesulfonates afford dimeric sulfone-sulfonate esters as well as products arising from SO bond rupture. SO bond rupture becomes more competitive as the LUMO energy of the sulfonate esterdeclines. Exploration of the chemistry of a sulfone-sulfonate ester revealed a complex novel reaction that resulted in the formation of, inter alia, a dichloromethanesulfonate ester and a trichloromethanesulfonate ester. The first successful approaches to the synthesis of the heretofore unknown trichloromethanesulfonates and dichloromethanesulfonates are reported. Introduction Phenyl methanesulfonate induces the condensation of ptoluenethiol and primary alcohols to afford sulfides (1). In pursuit of a variation of that approach to sulfide synthesis, phenyl benzenethiosulfonate was allowed to react with alkoxide ions. The expected sequence involved transformation of the thiosulfonate into a sulfonate ester and a thiolate anion with sequential thiolate anion alkylation by the newly formed sulfonate ester. Equation [I] depicts the outcome of such an experiment.

Sulfonyl esters 7. The second and third sequences in the Trithioorthoformate Reaction

“…The chemistry of sulfenes has been the subject of a recent review (1 1). Sulfonic acid esters are well-established presursors for the formation of sulfenes (1,12). Attack by mercaptide anions at the sulfene carbon (Scheme 6) is known as "carbophilic" attack (1 1) and has ample precedent (13).…”