Hectogram-Scale Synthesis of Carbamates Using Electrochemical Hofmann Rearrangement in Flow
The Hofmann rearrangement of alkyl and aryl carboxamides can be achieved electrochemically on a hectogram scale. The necessary halogen species and base equivalents are generated from sodium bromide in methanol by electrolysis. Both the supporting electrolyte and the solvent fulfill the role of mediator, conductivity-enabling agent, and reaction partners. This electrochemical conversion can be carried out in simple and commercially available plate-frame cells if a simple glassy carbon anode is used. A productivity of 104 mmol per h is obtained with 162 cm<sup>2</sup> of anode surface.
Authors
- Athanassios Ziogas (ORCID: https://orcid.org/0000-0002-9373-8674)
- Darryl F. Nater (ORCID: https://orcid.org/0000-0001-5800-3982)
- Rong Zhao (ORCID: https://orcid.org/0000-0003-2816-6777)
- B. Werner
- Siegfried R. Waldvogel (ORCID: https://orcid.org/0000-0002-7949-9638)
- Johannes Rocker (ORCID: https://orcid.org/0000-0001-8334-3807)
- Patrick Löb
- Coline Boche
- Dabeen Yun
Institutions
- Karlsruhe Institute of Technology (DE)
- Boehringer Ingelheim (Germany) (DE)
- Fraunhofer Institute for Microengineering and Microsystems (DE)
- Max Planck Institute for Chemical Energy Conversion (DE)
Publication Details
- Journal
- Organic Process Research & Development
- Published
- 2025-08-12
- DOI
- https://doi.org/10.1021/acs.oprd.5c00234
- Citations
- 4
- Primary Topic
- Radical Photochemical Reactions
- Type
- article
- Field-Weighted Citation Impact
- 3.74
Funders
- Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung
- Bundesministerium für Bildung und Forschung