Quinone-mediated hydrogen anode for non-aqueous reductive electrosynthesis

Jack Twilton, Mathew R. Johnson, Vinayak Sidana, Mareena C. Franke, Cecilia Bottecchia, Dan Lehnherr, François Lévesque, Spring M. M. Knapp, Luning Wang, James B. Gerken, Cynthia M. Hong, Thomas P. Vickery, Mark D. Weisel, Neil A. Strotman, Daniel J. Weix (), Thatcher W. Root () and Shannon S. Stahl ()
Additional contact information
Jack Twilton: University of Wisconsin–Madison
Mathew R. Johnson: University of Wisconsin–Madison
Vinayak Sidana: University of Wisconsin–Madison
Mareena C. Franke: University of Wisconsin–Madison
Cecilia Bottecchia: Merck & Co., Inc.
Dan Lehnherr: Merck & Co., Inc.
François Lévesque: Merck & Co., Inc.
Spring M. M. Knapp: University of Wisconsin–Madison
Luning Wang: University of Wisconsin–Madison
James B. Gerken: University of Wisconsin–Madison
Cynthia M. Hong: Merck & Co., Inc.
Thomas P. Vickery: Merck & Co., Inc.
Mark D. Weisel: Merck & Co., Inc.
Neil A. Strotman: Merck & Co., Inc.
Daniel J. Weix: University of Wisconsin–Madison
Thatcher W. Root: University of Wisconsin–Madison
Shannon S. Stahl: University of Wisconsin–Madison

Nature, 2023, vol. 623, issue 7985, 71-76

Abstract: 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, H2 represents an ideal alternative, motivating the growing interest in the electrochemical hydrogen oxidation reaction (HOR) under non-aqueous conditions7–12. Here we report a mediated H2 anode that achieves indirect electrochemical oxidation of H2 by pairing thermal catalytic hydrogenation of an anthraquinone mediator with electrochemical oxidation of the anthrahydroquinone. This quinone-mediated H2 anode 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 H2 anode technology disclosed here offers a general strategy to support H2-driven electrosynthetic reductions.

Date: 2023
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DOI: 10.1038/s41586-023-06534-2

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