Synthesis of α-Cyano-β-naphthylamines via Tandem Selective Hydrocyanation of Unactivated Alkynes and Thorpe Reaction

Abstract An unprecedented nickel-catalyzed tandem reaction involving alkyne hydrocyanation and sequential Thorpe reaction has been developed. By employing readily available and less toxic Zn(CN)2 as the cyanide source, both selective alkyne hydrocyanation and tandem cyclization are achieved in a substrate-controlled manner. Mechanistic studies and DFT calculations confirm that the alkenyl nitrile serves as a key intermediate, and hydrogen transfer is identified as the rate-determining step in the Thorpe reaction. This work offers a novel strategy for the construction of α-cyano-β-naphthylamine via a cascade reaction mode.