An unprecedented radical (phenylsulfonyl)difluoromethylation of terminal alkenes with PhSO2CF2I has been achievedby using Et3B/air as an initiator. This synthetic methodologywas also used in the one-pot regioselective preparation ofPhSO2CF2-substituted alkanes, and in the regio- and stereoselective preparation of PhSO2CF2-substituted alkenes withhigh E/Z ratio (up to ≥100:1).
