Copper-Promoted Cyclization of α‑Amino Nitrile-Tethered Enynes: Controllable Synthesis of 3‑Azabicyclo[4.1.0]hepta-2,4-dienes and 4,5-Dihydro‑3H‑azepines

The first example of Cu-promoted cyclization of α-amino nitrile-tethered enynes incorporating an electron-deficient alkene component is described. A wide range of functionalized 3-azabicyclo[4.1.0]­hepta-2,4-dienes and 4,5-dihydro-3H-azepines were prepared efficiently in a controllable manner. Moreover, the diverse cascade process enables efficient incorporation of tertiary amine moieties under mild reaction conditions. A possible reaction pathway is proposed on the basis of a series of control experiments.