Phenyl sulfones bearing an ortho dimethylsilyl group capable of conversion to the aryldimethylsilyl triflate moiety display significantly enhanced leaving group ability relative to simple phenyl sulfones. Under mild acid catalyzed conditions, ortho-allyldimethylsilyl sulfone 1b forms cyclic sultinium intermediate 2, which readily eliminates to provide olefins and a previously unreported cyclic silyl sulfinate by-product, 4, orto-Allyldimethylsilyl aryl sulfones are easily prepared via ortho-allyldimethylsilyl mercaptide anion 5 and serve as the latent precursor of the activated silyltriflate intermediate. The sulfone elimination proceeds in high yield under mild conditions whether or not activated beta-protons are present in the substrate. An attempt to effect intramolecular Friedel-Crafts alkylation via the interception of sultinium intermediate 17 resulted in formation of tricyclic olefin 22 as the major product.