NDLI: Computational exploration of the mechanism of copper-catalyzed aromatic C–H bond amination of benzene via a nitrene insertion approach

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Bao, Xiaoguang Hou, Kaipeng Hrovat, David A.
Description	Author Affiliation: Hou K ( College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou Industrial Park, Suzhou, Jiangsu 215123, China. xgbao@suda.edu.cn.);
Abstract	The mechanism of aromatic C–H amination of benzene via a nitrene insertion approach catalyzed by the $Tp^{Br3}Cu(NCMe)$ complex was computationally investigated. The results of computational studies show that addition of the nitrene moiety of the $Tp^{Br3}Cu–nitrene$ intermediate to benzene, and therefore, to form an aziridine intermediate, is more favorable than the nitrene moiety induced hydrogen atom abstraction from a $sp^{2}$ C–H bond of benzene. Subsequently, the cleavage of a C–N bond of the aziridine intermediate followed by an H-atom transfer step might occur, due to the driving force of the rearomatization, to afford the desired aromatic C–H amination product. For toluene, computational results suggest that the benzylic C–H amination via hydrogen atom abstraction followed by radical rebound path is more favorable than the aromatic C–H amination via a nitrene addition path, which is in accord with experimental results.
ISSN	13597345
Volume Number	51
Journal	Chemical Communications
Issue Number	84
e-ISSN	1364548X
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-10-01
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Ceramics and Composites Chemistry Surfaces, Coatings and Films Materials Chemistry Metals and Alloys Electronic, Optical and Magnetic Materials Catalysis

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