Abstract: | A copper‐catalyzed three‐component reaction of alkenes, acetonitrile, and sodium azide afforded γ‐azido alkyl nitriles by formation of one C(sp3)−C(sp3) bond and one C(sp3)−N bond. The transformation allows concomitant introduction of two highly versatile groups (CN and N3) across the double bond. A sequence involving the copper‐mediated generation of a cyanomethyl radical and its subsequent addition to an alkene, and a C(sp3)−N bond formation accounted for the reaction outcome. The resulting γ‐azido alkyl nitrile can be easily converted into 1,4‐diamines, γ‐amino nitriles, γ‐azido esters, and γ‐lactams of significant synthetic value. |