Cu/Ni-Catalyzed Cyanomethylation of Alkenes with Acetonitrile for the Synthesis of β,γ-Unsaturated Nitriles

We have developed a protocol for the Cu/Ni-catalyzed cyanomethylation of alkenes with acetonitrile for the synthesis of β,γ-unsaturated nitriles. This is the first example of a direct coupling of the alkene sp2 C—H bond and the acetonitrile sp3 C—H bond for the preparation of β,γ-unsaturated nitriles. Acetonitrile, an inexpensive and stable solvent, is demonstrated to be a useful cyanomethyl source. The combination of copper and nickel catalysts resulted in a high reaction efficiency.