[4+2] Defluorocycloaddition of Perfluoroalkyl Alkynes and Benzylamines: Synthesis of <i>meta</i>-Fluoroalkylated Pyridin-4-amines

Pyridines represent privileged heterocycles, and the ability to produce fluorinated pyridines from polyfluorinated substances through selective defluorofunctionalization is a new addition to their synthesis. Herein, an unprecedented formal [4+2] defluorocycloaddition of perfluoroalkyl alkynes and benzylamines under metal-free conditions is described. By leveraging the functionalization of four C(sp³)-F bonds on two vicinal sterically hindered perfluoroalkyl carbons of perfluoroalkyl alkynes, a diverse array of <i>meta</i>-fluoroalkylated pyridin-4-amines were synthesized with good functional group tolerance. The mechanistic studies revealed a sequence of hydroamination, successive defluorination, 6π-electrocyclization, aromatization, and amination.