The first general and regioselective nickel-catalyzed hydrocyanation of terminal alkenes with Zn(CN)2 using an air-stable and inexpensive nickel(II) salt as the precatalyst has been established. The strategy avoids the use of the volatile and hazardous reagent HCN. Aryl/heteroaryl alkenes are effectively converted to branched nitrile derivatives, while aliphatic alkenes or active alkenes are transformed to linear nitriles with good to excellent regioselectivity.

