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The Mechanism of Rhodium-Catalyzed Allylic C-H Amination
Authors
Cora E. MacBeth
Daniel C. Salgueiro
+7 more
Jiyong Park
John Bacsa
Mu-Hyun Baik
Nafees Iqbal
Robert J. Harris
Simon B. Blakey
Taylor A. F. Nelson
Publication date
1 March 2020
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 Societ
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Last time updated on 29/10/2020