The Mechanism of Rhodium-Catalyzed Allylic C-H Amination

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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(p-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 pi-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.
Publisher
AMER CHEMICAL SOC
Issue Date
2020-03
Language
English
Article Type
Article
Citation

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.142, no.12, pp.5842 - 5851

ISSN
0002-7863
DOI
10.1021/jacs.0c01069
URI
http://hdl.handle.net/10203/274143
Appears in Collection
CH-Journal Papers(저널논문)
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