Catalytic Role of Methanol in Anodic Coupling Reactions Involving Alcohol Trapping of Cation Radicals.

ABSTRACT: In anodic electrosynthesis, cation radicals are often key intermediates that can be highly susceptible to nucleophilic attack and/or deprotonation, with the selectivity of competing pathways dictating product yield. In this work, we computationally investigate the role of methanol in alcohol trapping of enol ether cation radicals for which substantial modulation of the reaction yield by the solvent environment was previously observed. Reaction free energies computed for intramolecular coupling unequivocally demonstrate that the key intramolecular alcohol attack on the oxidized enol ether group is catalyzed by methanol, proceeding through overall second-order kinetics. Methanol complexation with the formed oxonium ion group gives rise to a "Zundel-like", shared proton conformation, providin

SUBMITTER: Khan SN 

PROVIDER: S-EPMC11667722 | biostudies-literature | 2024 Dec

REPOSITORIES: biostudies-literature