Enantioselective CH Bond Functionalization Triggered by Radical Trifluoromethylation of Unactivated Alkene

An asymmetric unactivated alkene/CH bond difunctionalization reaction for the concomitant construction of CCF 3 and CO bonds was realized by using a Cu/Brønsted acid cooperative catalytic system, thus providing facile access to valuable chiral CF 3 ‐containing N,O‐aminals with excellent regio‐, chemo‐, and enantioselectivity. Mechanistic studies revealed that this reaction may proceed by an unprecedented 1,5‐hydride shift involving activation of unactivated alkenes and a radical trifluoromethylation to initiate subsequent enantioselective functionalization of CH bonds. Control experiments also suggested that chiral Brønsted acid plays multiple roles and not only controls the stereoselectivity but also increases the reaction rate through activation of Togni’s reagent.