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 Rh(esp) 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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