Electrifying oxygen atom transfer reactions: utilizing pathways of OER and ORR for organic synthesis

Oxygen atom transfer (OAT) reactions are key transformations in the synthesis of commodity and fine chemicals, with existing processes relying on stoichiometric oxidants and sometimes harsh reaction conditions. Electrification enables these reactions (e-OAT) to occur at room temperature and replaces chemical oxidants with low-cost electricity using sustainable O atom donors such as water or O₂ to reduce environmental impact. At the same time, e-OAT separates the thermodynamic driving force provided by electricity from the oxygen atom source, providing potential for a unique selectivity that cannot easily be achieved in traditional methods using chemical oxidants. In order to spark new developments in the field of e-OAT, this Perspective summarizes the fundamental mechanistic aspects and successful examples of chemical OAT to highlight the relation as well as the development potential of e-OAT reactions across epoxidation, C-H hydroxylation, sulfoxidation, N-oxidation and phosphine oxidation. Covering both homogeneous and heterogeneous catalysts, the state-of-the-art and most recent developments of these e-OAT reactions are included herein. We elaborate on the role of different reactive intermediate types and the design principles for catalysts and reaction conditions, outlining ways to achieve high reaction selectivity for e-OAT processes over parasitic side reactions such as O₂ evolution, as well as the strategies for facilitating challenging reactions such as partial methane oxidation to methanol. To inspire innovation, we visualize an overlap of the active intermediates of e-OAT with OER and ORR catalysis platforms, with an opportunity for repurposing the existing successful catalysts for e-OAT. Finally, we showcase with selected examples that the successful application of e-OAT catalysis will eventually require combined control over catalyst species as well as reactor design to accomplish demanding target reactions, such as epoxidation, methane hydroxylation or oxidative N₂ fixation, at optimal performance.