An expeditious entry to benzylic and allylic sulfones through byproduct-catalyzed reaction of alcohols with sulfinyl chlorides.

In the absence of external catalysts and additives, a broad range of benzylic and allylic alcohols react with various sulfinyl chlorides to afford structurally diversified benzylic and allylic sulfones in moderate to excellent yields, and importantly, a catalysis with byproduct HCl is involved in this new protocol for sulfone synthesis.