Mechanism (biology)

Catalysis

Philosophy

Allylic rearrangement

Photochemistry

Rhodium

Reaction mechanism

Receptor

Biochemistry

Lewis acids and bases

Medicinal chemistry

Combinatorial chemistry

Ligand (biochemistry)

Organic chemistry

Stoichiometry

Amination

Epistemology

Catalytic cycle

Chemistry

Journal of the American Chemical Society

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.

The Mechanism of Rhodium-Catalyzed Allylic C–H Amination