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Updated: Jul 20, 2025

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
Published on: November 29, 2018
Rhodium-Catalyzed Intramolecular Nitrogen Atom Insertion into Arene Rings
Hang Li1, Na Li2, Jinghao Wu1
1Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an 710069, China.
Abstract:
In this study, we describe the direct insertion of an intramolecular nitrogen atom into an aromatic C-C bond. In this transformation, carbamoyl azides are activated by a Rh catalyst and subsequently directly inserted into the C-C bond of an arene ring to access fused azepine products. This transformation is challenging, owing to the existence of a competitive C-H amination pathway. The use of a paddlewheel dirhodium complex Rh2(esp)2 effectively inhibited the undesired C-H insertion. Density functional theory calculations were performed to reveal the reaction mechanism and origin of the chemoselectivity of the Rh-catalyzed reactions. The novel fused azepine products are highly robust and allow for downstream diversification.
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