1. Quinone-mediated hydrogen anode for non-aqueous reductive electrosynthesis
- Author
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Twilton, Jack, Johnson, Mathew R., Sidana, Vinayak, Franke, Mareena C., Bottecchia, Cecilia, Lehnherr, Dan, Lévesque, François, Knapp, Spring M. M., Wang, Luning, Gerken, James B., Hong, Cynthia M., Vickery, Thomas P., Weisel, Mark D., Strotman, Neil A., Weix, Daniel J., Root, Thatcher W., and Stahl, Shannon S.
- Abstract
Electrochemical synthesis can provide more sustainable routes to industrial chemicals1–3. Electrosynthetic oxidations may often be performed ‘reagent-free’, generating hydrogen (H2) derived from the substrate as the sole by-product at the counter electrode. Electrosynthetic reductions, however, require an external source of electrons. Sacrificial metal anodes are commonly used for small-scale applications4, but more sustainable options are needed at larger scale. Anodic water oxidation is an especially appealing option1,5,6, but many reductions require anhydrous, air-free reaction conditions. In such cases, H2represents an ideal alternative, motivating the growing interest in the electrochemical hydrogen oxidation reaction (HOR) under non-aqueous conditions7–12. Here we report a mediated H2anode that achieves indirect electrochemical oxidation of H2by pairing thermal catalytic hydrogenation of an anthraquinone mediator with electrochemical oxidation of the anthrahydroquinone. This quinone-mediated H2anode is used to support nickel-catalysed cross-electrophile coupling (XEC), a reaction class gaining widespread adoption in the pharmaceutical industry13–15. Initial validation of this method in small-scale batch reactions is followed by adaptation to a recirculating flow reactor that enables hectogram-scale synthesis of a pharmaceutical intermediate. The mediated H2anode technology disclosed here offers a general strategy to support H2-driven electrosynthetic reductions.
- Published
- 2023
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