Rh(III)-Catalyzed Atroposelective C–H Cyanation of 1-Aryl benzo[<i>h</i>]isoquinolines

The atroposelective C-H cyanation of 1-aryl isoquinolines using rhodium(III) catalysis was realized. In the presence of a chiral binaphthyl "O"-linked Cp rhodium (BOCpRh) complex, highly atroposelective C-H cyanation of 1-aryl isoquinolines with <i>N</i>-cyano-<i>N</i>-phenyl-<i>p</i>-toluenesulfonamide proceeded smoothly to afford a wide range of axially chiral 1-aryl isoquinoline nitriles in up to 94% yield and 91% ee. This method provides a facile access to axially chiral nitriles under mild conditions. The transformations of the products and preliminary mechanistic studies have been carried out.