At low temperature, 1-alkoxy-1,3-dienes add to sulfur dioxide activated by a Lewis or protic acid generating zwitterionic intermediates that can be quenched by enoxysilanes. The resulting beta,gamma-unsaturated silyl sulfinates can be desilylated by 1:1 Pd(OAc)(2)/PPh3 catalyst, liberating the corresponding beta,gamma-unsaturated sulfinic acids that undergo smooth and highly stereoselective retro-ene eliminations of sulfur dioxide. The method has been applied to generate enantiomerically pure polypropionate fragments.