Health & Environmental Research Online (HERO)


Print Feedback Export to File
4276594 
Journal Article 
Computational exploration of the mechanism of copper-catalyzed aromatic C-H bond amination of benzene via a nitrene insertion approach 
Hou, K; Hrovat, DA; Bao, X 
2015 
Yes 
Chemical Communications
ISSN: 1359-7345
EISSN: 1364-548X 
51 
84 
15414-15417 
English 
26343255 
WOS:000363167600015 
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.