Rhodium-Catalyzed Intramolecular Nitrogen Atom Insertion into Arene Rings

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 transform...

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Published inJournal of the American Chemical Society Vol. 145; no. 32; pp. 17570 - 17576
Main Authors Li, Hang, Li, Na, Wu, Jinghao, Yu, Tianyang, Zhang, Ran, Xu, Li-Ping, Wei, Hao
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 16.08.2023
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
FUNCTIONALIZATION
DESIGN
CYCLIZATIONS
BENZENE
AZIDOFORMATES
BONDS
CHEMISTRY
INHIBITORS
C-H AMINATION
NITRENE
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Summary: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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ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.3c07640