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분자활성 촉매반응 연구단
분자활성 촉매반응 연구단
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Mechanistic Studies of the Rhodium-Catalyzed Direct C–H Amination Reaction Using Azides as the Nitrogen Source Highly Cited Paper

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Title
Mechanistic Studies of the Rhodium-Catalyzed Direct C–H Amination Reaction Using Azides as the Nitrogen Source
Author(s)
Sae Hume Park; Jaesung Kwak; Kwangmin Shin; Jaeyune Ryu; Yoonsu Park; Suk Bok Chang
Publication Date
2014-02
Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.136, no.6, pp.2492 - 2502
Publisher
AMER CHEMICAL SOC
Abstract
Direct C-H amination of arenes offers a straightforward route to aniline compounds without necessitating aryl (pseudo)halides as the starting materials. The recent development in this area, in particular in the metal-mediated transformations, is significant with regard to substrate scope and reaction conditions. Described herein are the mechanistic details on the Rh-catalyzed direct C-H amination reaction using organic azides as the amino source. The most important two stages were investigated especially in detail: (i) the formation of metal nitrenoid species and its subsequent insertion into a rhodacycle intermediate, and (ii) the regeneration of catalyst with concomitant release of products. It was revealed that a stepwise pathway involving a key Rh(V)-nitrenoid species that subsequently undergoes amido insertion is favored over a concerted C-N bond formation pathway. DFT calculations and kinetic studies suggest that the rate-limiting step in the current C-H amination reaction is more closely related to the formation of Rh-nitrenoid intermediate rather than the presupposed C-H activation process. The present study provides mechanistic details of the direct C-H amination reaction, which bears both aspects of the inner- and outer-sphere paths within a catalytic cycle. © 2014 American Chemical Society.
URI
https://pr.ibs.re.kr/handle/8788114/1129
ISSN
0002-7863
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
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