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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...
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