Development of a New Carbon−Carbon Bond Forming Reaction. New Organic Chemistry of Sulfur Dioxide. Asymmetric Four-Component Synthesis of Polyfunctional Sulfones

Abstract

At low temperature 1-alkoxy-1,3-dienes add to sulfur dioxide activated by a Lewis or Brønstedt acid and generate zwitterionic intermediates that can be quenched by enoxysilanes. The resulting beta,gamma-unsaturated silyl sulfinates can be desilylated and reacted with methyl iodide to provide polyfunctional sulfones. Exploratory studies of this four-component synthesis of sulfones are reported. Enantiomerically pure derivatives containing up to three new stereogenic centers can be obtained using enantiomerically pure (E,E)-1-alkoxy-2-methylpenta-1,3-dienes derived from alpha-methyl benzyl alcohols, including the Greene's chiral auxiliary. The stereochemistry of the reactions is consistent with a mechanism involving the suprafacial hetero-Diels-Alder addition of sulfur dioxide to the 1-alkoxy-1,3-dienes that are rapidly ionized into zwitterionic intermediates.