Copper-Mediated Amination of Aryl C-H Bonds with the Direct Use of Aqueous Ammonia via a Disproportionation Pathway

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Title
Copper-Mediated Amination of Aryl C-H Bonds with the Direct Use of Aqueous Ammonia via a Disproportionation Pathway
Author(s)
Hyunwoo Kim; Joon Heo; Junho Kim; Mu-Hyun Baik; Sukbok Chang
Publication Date
2018-10
Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.140, no.43, pp.14350 - 14356
Publisher
AMER CHEMICAL SOC
Abstract
The direct amination of C-H bonds with ammonia is a challenge in synthetic chemistry. Herein, we present a copper-mediated approach that enables a chelation-assisted aromatic C-H bond amination using aqueous ammonia. A key strategy was to use soft low-valent Cu(I) species to avoid the strong coordination of ammonia. Mechanistic investigations suggest that the catalysis is initiated by a facile deprotonation of bound ammonia, and the C-N coupling is achieved by subsequent reductive elimination of the resultant copper-amido intermediate from a Cu(III) intermediate that is readily generated by disproportionation of low-valent copper analogues. This mechanistic postulate was supported by a preliminary kinetic isotope effect study and computations. This new chelation-assisted, copper-mediated C-H bond amination with aqueous ammonia was successfully applied to a broad range of substrates to deliver primary anilines. Moreover, the mild conditions required for this transformation allowed the reaction to operate even under substoichiometric conditions to enable a late-stage application for the preparation of pharmaceutical agents. © 2018 American Chemical Society
URI
https://pr.ibs.re.kr/handle/8788114/5133
ISSN
0002-7863
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
Files in This Item:
C_jacs.8b08826(Copper-Mediated Amination of Aryl).pdfDownload

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