Mechanistic Studies of the Rhodium-Catalyzed Direct C-H Amination Reaction Using Azides as the Nitrogen Source

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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.
Publisher
AMER CHEMICAL SOC
Issue Date
2014-02
Language
English
Article Type
Article
Keywords

N BOND FORMATION; TRANSITION-METAL-COMPLEXES; INDUCED REDUCTIVE ELIMINATIONS; ARYL AZIDES; ORGANIC AZIDES; AMBIENT-TEMPERATURE; SULFONYL AZIDES; INTERMOLECULAR AMINATION; INTRAMOLECULAR AMIDATION; HETEROCYCLE SYNTHESIS

Citation

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.136, no.6, pp.2492 - 2502

ISSN
0002-7863
DOI
10.1021/ja411072a
URI
http://hdl.handle.net/10203/190187
Appears in Collection
CH-Journal Papers(저널논문)
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