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

Title
Mechanistic Studies of the Rhodium-Catalyzed Direct C-H Amination Reaction Using Azides as the Nitrogen Source
Authors
Sae Hume ParkJaesung KwakKwangmin Shin류재윤Yoonsu ParkSukbok Chang
Issue Date
2014-01
Publisher
Journal of the American Chemical Society
Citation
VOL 136, 2492-2502
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 metalmediated 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.
URI
http://pubs.kist.re.kr/handle/201004/48555
ISSN
00027863
Appears in Collections:
KIST Publication > Article
Files in This Item:
There are no files associated with this item.
Export
RIS (EndNote)
XLS (Excel)
XML


qrcode

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

BROWSE