Rh(III)-Catalyzed Atroposelective C–H Cyanation of 1‑Aryl benzo[h]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 N-cyano-N-phenyl-p-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.