(472c) Electrochemical Oxygen-Atom Transfer Reactions

Oxygen-atom functionalization of chemical intermediates is critical for the production of diverse textiles, plastics, and pharmaceuticals, including epoxides and ketones. The wet chemical and thermochemical routes used today suffer from large carbon dioxide footprints, stoichiometric waste products, and hazardous reagents. We have developed a route whereby water can be used as the oxygen atom source in functionalization reactions including epoxidation. At the cathode, hydrogen is selectively generated. Overall, this reaction provides a means by which the oxidizing equivalents can go towards generating a valuable product rather than generating oxygen which is simply vented in a conventional water electrolyzer. We have developed mechanistic understanding of how water is oxidized, providing means by which the selectivity for oxygen-atom functionalization can be rationally improved.