The homoallylic alcohols 3 that can be prepared by the indium-mediated addition of haloallylic sulfones 1 to aldehydes 2 undergo the oxonia-Cope rearrangement with aldehydes 2 to give rise to the allylic sulfones 4 containing a conjugated diene moiety in a highly stereoselective manner. Electron-rich aldehydes preferentially participate in this oxonia-Cope rearrangement with the homoallylic alcohols 3. Excellent correlations of the stereochemistry (anti-3 to trans-allylic sulfone 4 and syn-3 to cis-allylic sulfone 4) have been observed in the oxonia-Cope rearrangement.
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