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 beta,gamma-unsaturated nitriles. This is the first example of a direct coupling of the alkene sp(2) C-H bond and the acetonitrile sp(3) C-H bond for the preparation of beta,gamma-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.