Lanthanide-Catalyzed Tandem Insertion of Secondary Amines with 2-Alkynylbenzonitriles: Synthesis of Aminoisoindoles.

A lanthanide-catalyzed intermolecular hydroamination of 2-alkynylbenzonitriles with secondary amines has been disclosed, providing a streamlined access to a range of aminoisoindoles in moderate to excellent yields. The salient features of this reaction include high bond-formation efficiency, mild reaction conditions, 100 % atomic efficiency and good functional group tolerance. This methodology has also been successfully applied to the construction of other nitrogen-containing compounds, such as 5 H-imidazo[2,1-a]isoindoles and isoquinolines. A plausible mechanism for the formation of aminoisoindoles involving initial N-H activation by a lanthanide complex followed by C≡N insertion into a Ln-N bond to form an amidinate lanthanide intermediate, which undergoes the cyclization is proposed.