An unprecedented radical (phenylsulfonyl)difluoromethylation of terminal alkenes with PhSO
2CF
2I has been achievedby using Et
3B/air as an initiator. This synthetic methodologywas also used in the one-pot regioselective preparation ofPhSO
2CF
2-substituted alkanes, and in the regio- and stereoselective preparation of PhSO
2CF
2-substituted alkenes withhigh
E/
Z ratio (up to
100:1).