Sequential Addition of Amines to Nitrile and Carbon-Carbon Multiple Bond: A Route to 7-Amino-5H-dibenzo[c,e]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.