A Catalytic Three‐Component Aminofluorination of Unactivated Alkenes with Electron‐Rich Amino Sources

Abstract We present herein a copper‐catalyzed three‐component aminofluorination of unactivated alkenes with N‐bromodialkylamines and readily available nucleophilic fluoride under the assistance of a bidentate auxiliary. This protocol exhibits excellent functional group tolerance toward a wide range of unactivated alkenes and N‐bromodialkylamines to furnish the corresponding β‐fluoroalkylamines in a highly regio‐ and diastereoselective manner. The appropriate choice of nucleophilic fluoro source is essential to make this reaction a reality. Further DFT calculations show that the exothermic ion exchange between external fluoride ion and Cu(II) intermediate provides additional driving force to the irreversible migratory insertion, which offsets the unfavorable reaction energetics associated with the subsequent C(sp³)–F reductive elimination. This finding offers a new avenue to catalytic intermolecular aminofluorination of unactivated alkenes with electron‐rich amino sources via a remarkable reductive elimination of Cu(III) species to forge the C(sp³)–F bonds.