Anthranil: An Aminating Reagent Leading to Bifunctionality for Both C(sp3)−H and C(sp2)−H under Rhodium(III) Catalysis

Previous direct C−H nitrogenation suffered from simple amidation/amination with limited atom‐economy and is mostly limited to C(sp2)−H substrates. In this work, anthranil was designed as a novel bifunctional aminating reagent for both C(sp2)−H and C(sp3)−H bonds under rhodium(III) catalysis, thus af...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2016-07, Vol.55 (30), p.8696-8700
Main Authors: Yu, Songjie, Tang, Guodong, Li, Yingzi, Zhou, Xukai, Lan, Yu, Li, Xingwei
Format: Article
Language:English
Subjects:
amination
arenes
Catalysis
C−H activation
reaction mechanisms
rhodium
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Summary:Previous direct C−H nitrogenation suffered from simple amidation/amination with limited atom‐economy and is mostly limited to C(sp2)−H substrates. In this work, anthranil was designed as a novel bifunctional aminating reagent for both C(sp2)−H and C(sp3)−H bonds under rhodium(III) catalysis, thus affording a nucleophilic aniline tethered to an electrophilic carbonyl. A tridendate rhodium(III) complex has been isolated as the resting state of the catalyst, and DFT studies established the intermediacy of a nitrene species. Double agent: Anthranil was designed as a novel bifunctional aminating reagent for both C(sp2)−H and C(sp3)−H bonds under rhodium(III) catalysis, thus affording a nucleophilic aniline tethered to an electrophilic carbonyl. A tridendate rhodium(III) complex was isolated as the resting state of the catalyst, and DFT studies established the intermediacy of a nitrene species.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201602224