Ligand-Controlled Ni-Catalyzed Regiodivergent Hydrocyanation of Unactivated Alkynes toward Linear and Branched Vinyl Nitriles

In this paper, we have developed an efficient Ni-catalyzed highly regioselective and stereoselective hydrocyanation of alkynes and Zn(CN)2. By the control of different ligands, nickel-catalyzed regiodivergent hydrocyanation of terminal alkynes to linear and branched vinyl nitriles via anti-Markovnikov and Markovnikov additions was achieved. In addition, in this system, water or alcohol served as the hydrogen source, thus avoiding the in-situ generation of hydrogen cyanide in the reaction. A preliminary study of the mechanism was performed by deuterium labeling experiments and several control experiments.