Sulfination of Unactivated Allylic Alcohols via Sulfinate-Sulfone Rearrangement.

A dehydrative cross-coupling of unactivated allylic alcohols with sulfinic acids was achieved under catalyst-free conditions. This reaction proceeded via allyl sulfination and concomitant allyl sulfinate-sulfone rearrangement. Various allylic sulfones could be obtained in good to excellent yields with water as the only byproduct. This study expands the synthetic toolbox for constructing allylic sulfone molecules.