Enantioselective Formation of Cyano‐Bearing All‐Carbon Quaternary Stereocenters: Desymmetrization by Copper‐Catalyzed N‐Arylation

Abstract The enantioselective construction of all‐carbon quaternary stereocenters is one of the most challenging fields in asymmetric synthesis. An asymmetric desymmetrization strategy offers an indirect and efficient method for the formation of all‐carbon stereocenters. An enantioselective formation of cyano‐bearing all‐carbon quaternary stereocenters in 1,2,3,4,‐tetrahydroquinolines and 2,3,4,5‐tetrahydro‐1H‐benzo[b]azepines by copper‐catalyzed desymmetric N‐arylation is demonstrated. The cyano group at the prochiral center plays a key role for the high enantioselectivity and works as an important functional group for further transformations. DFT studies provide a model which successfully accounts for the origin of enantioselectivity.