Chiral hydrogen-bonding (H-bonding) catalytic asymmetric conjugate addition to activated olefins has been widely used to access enantioenriched molecules containing stereocenters at the β-position of the olefin activating groups. Herein, we report the first highly enantioselective radicalbased manifold. Under a dual organocatalyst system involving a chiral phosphoric acid and DPZ as the photoredox sensitizer, transformations of N-arylglycines, in which aryls with CF 3 substituents are introduced, with alkenyl azaarenes afforded valuable hydroaminoalkylation adducts with satisfactory results. In addition to the diversity of azaarenes, the method can be used to construct aryl-, alkyl-and silylsubstituted stereocenter. Control experiments and density functional theory calculations were performed to elucidate a plausible reaction mechanism and the origin of stereoselectivity, wherein nonclassical H-bonding interactions were found to assist chiral catalysts in offering sufficient enantiocontrol.

Chiral hydrogen‐bonding (H‐bonding) catalytic asymmetric conjugate addition to activated olefins has been widely used to access enantioenriched molecules containing stereocenters at the β‐position of the olefin activating groups. Herein, we report the first highly enantioselective radical‐based manifold. Under a dual organocatalyst system involving a chiral phosphoric acid and DPZ as the photoredox sensitizer, transformations of N‐arylglycines, in which aryls with CF3 substituents are introduced, with alkenyl azaarenes afforded valuable hydroaminoalkylation adducts with satisfactory results. In addition to the diversity of azaarenes, the method can be used to construct aryl‐, alkyl‐ and silyl‐substituted stereocenter. Control experiments and density functional theory calculations were performed to elucidate a plausible reaction mechanism and the origin of stereoselectivity, wherein nonclassical H‐bonding interactions were found to assist chiral catalysts in offering sufficient enantiocontrol.