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submitted on 01.09.2019 and posted on 04.09.2019by Robert Harris, Jiyong Park, Taylor Nelson, Nafees Iqbal, Daniel Salgueiro, John Bacsa, Cora MacBeth, Mu-Hyun Baik, Simon Blakey
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 allylic C–H activation to generate a Cp*Rh(π-allyl) complex is viable under mild reaction conditions. The role of external oxidant in the catalytic cycle is elucidated. Quantum mechanical calculations, stoichiometric reactions, and cyclic voltammetryexperiments support an oxidatively induced reductive elimination process of the allyl fragment with an acetate ligand. Lastly, evidences supporting the amination of an allylic acetate intermediate is presented. Both nucleophilic substitution catalyzed by Ag+that behaves as a Lewis acid catalyst and an inner-sphere amination catalyzed by Cp*Rh are shown to be viable for the last step of the allylic amination reaction.