Formal 1,1-Hydrocyanation Reaction of Alkynyl Halides with Isocyanides Enabled by Dual Nickel/Base Catalysis Relay

We herein describe a formal 1,1-hydrocyanation reaction of alkynyl halides with isocyanides enabled by a dual nickel/base catalysis relay. <i>tert</i>-Butyl isocyanide serves as a "HCN" precursor that is introduced to the α-position of alkynyl halides, and the halogen atom is moved to the β-position. As a result, a series of (<i>Z</i>)-3-bromo/iodo acrylonitrile derivatives could be obtained in moderate yields. Mechanistic experiments were carried out, and the collective data could support our proposal of the mechanism details.