Asymmetric Hydroaminoalkylation of Alkenylazaarenes via Cooperative Photoredox and Chiral Hydrogen-Bonding Catalysis.

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 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 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.