Silyl enol ethers of esters, ketones, as well as allylstannane and allylsilanes react with sulfur dioxide activated with t-BuMe2SiOSO2CF3 to give silyl sulfinates that can be reacted in the same pot with a variety of electrophiles generating the corresponding polyfunctional sulfones. The silyl sulfinate intermediates are formed via ene-reactions following probably concerted mechanisms.