Catalytic Radical Intramolecular Aminoperfluoroalkylation and Aminodifluoromethylation of Unactivated Alkenes with Fluoro-alkylsulfonyl Chlorides

The Cu(I)/phosphoric acid (PA) dual-catalyzed radical aminoperfluoroalkylation and aminodifluoromethylation of alkenes with commercially available fluoroalkylsulfonyl chlorides as the radical source is described. Functionalized alpha-tertiary pyrrolidines bearing four types of fluoroalkyl groups are obtained with moderate to excellent yields. The introduction of a Cu(I)/phosphoric acid dual catalytic system and the use of silver carbonate as a key additive to inhibit the side hydroamination reaction caused by the in situ generated HCl are crucial for the transformation.