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The Mechanism of Rhodium-Catalyzed Allylic C-H Amination

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Title
The Mechanism of Rhodium-Catalyzed Allylic C-H Amination
Author(s)
Robert J. Harris; Jiyong Park; Taylor A. F. Nelson; Nafees Iqbal; Daniel C. Salgueiro; John Bacsa; Cora E. MacBeth; Mu-Hyun Baik; Simon B. Blakey
Publication Date
2020-03
Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.142, no.12, pp.5842 - 5851
Publisher
AMER CHEMICAL SOC
Abstract
Herein, the mechanism of catalytic allylic C-H amination reactions promoted by Cp*Rh complexes is reported. Reaction kinetics experiments, stoichiometric studies, and DFT calculations demonstrate that the allylic C-H activation to generate a Cp*Rh(π-allyl) complex is viable under mild reaction conditions. The role of external oxidants in the catalytic cycle is elucidated. Quantum mechanical calculations, stoichiometric reactions, and cyclic voltammetry experiments concomitantly support an oxidatively induced reductive elimination process of the allyl fragment with an acetate ligand proceeding through a Rh(IV) intermediate. Stoichiometric oxidation and bulk electrolysis of the proposed π-allyl intermediate are also reported to support these analyses. Lastly, evidence supporting the amination of an allylic acetate intermediate is presented. We show that Cp*Rh(III)2+ behaves as a Lewis acid catalyst to complete the allylic amination reaction. © 2020 American Chemical Society
URI
https://pr.ibs.re.kr/handle/8788114/7166
ISSN
0002-7863
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
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