Copper-catalyzed hydroamination of polyfluoroalkyl substituted alkenes via asymmetric radical cross-coupling access to α-chiral tertiary alkylamines

α-Chiral tertiary alkylamines are quintessential scaffolds in pharmaceuticals, bioactive molecules, and organic materials. Although there has been substantial advancement in the synthesis of chiral amides or sulfonamides through open-shell pathway in recent years, it remains problematic to efficiently obtain optically active aliphatic amines, especially α-chiral tertiary alkylamines. Herein, we have demonstrated, by means of density functional theory calculations jointly with experimental studies, that the chiral C–N bond can be forged through a mechanically unprecedented radical cross-coupling of a Cu(I)-bounded dialkyl amine radical species with a carbon-based radical species. Consequently, by virtue of this protocol, a diversity of important optically active β-polyfluoroalkyl substituted α-chiral tertiary alkylamines have been efficiently constructed with high enantioselectivity.