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The reaction of (E,E)-1-benzyloxy-2-methylpenta-1,3-diene with trimethylsilyl enol ethers derived from acetone or acetophenone with sulfur dioxide precomplexed with ytterbium triflate or (CF3SO2)(2)NH generates sulfinate intermediates that can be quenched by a variety of electrophiles to afford the corresponding polyfunctional sulfones in one-pot operations.