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

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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.
Publisher
AMER CHEMICAL SOC
Issue Date
2018-10
Language
English
Article Type
Article
Keywords

CROSS-COUPLING REACTIONS; CATALYZED AMINATION; PRIMARY AMINES; AMIDATION; PALLADIUM; HYDROGEN; ANILINES; ACTIVATION; COMPLEXES; CLEAVAGE

Citation

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.140, no.43, pp.14350 - 14356

ISSN
0002-7863
DOI
10.1021/jacs.8b08826
URI
http://hdl.handle.net/10203/247140
Appears in Collection
CH-Journal Papers(저널논문)
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