Sequential Addition of Amines to Nitrile and Carbon–Carbon Multiple Bond: A Route to 7‑Amino‑5<i>H</i>‑dibenzo[<i>c,e</i>]azepines

A rare earth metal-catalyzed sequential inter- and intramolecular C–N bond formation of 2-nitrile-2′-alkenyl­(alkynyl)­biphenyls with amines has been developed, which provides a straightforward and efficient access to a range of new functional dibenzo­[c,e]­azepines. This represents the first examples of direct construction of seven-membered azaheterocycle from unsaturated nitriles and amines. Such transformations have the advantages of avoiding the use of additives, easily available starting materials, step- and high atom-economy, mild reaction conditions, and high selectivity