Overcoming the limitations of Kolbe coupling with waveform-controlled electrosynthesis

• 成果类型: Article
• 署名作者: Hioki, Yuta; Costantini, Matteo; Griffin, Jeremy; Harper, Kaid C.; Merini, Melania Prado; Nissl, Benedikt; Kawamata, Yu; Baran, Phil S.
• 署名单位: Scripps Research Institute; Mitsubishi International Corporation (MIC); Mitsubishi Chemical Holdings Corporation; Mitsubishi Chemical
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-13324
• DOI: 10.1126/science.adf4762
• 发表日期: 2023-04-07
• 关键词: synthetic applications; acid-derivatives; polymers; analogs; biomass; electrolysis; inhibitor; chemistry; peptides; homologs

摘要

The Kolbe reaction forms carbon-carbon bonds through electrochemical decarboxylative coupling. Despite more than a century of study, the reaction has seen limited applications owing to extremely poor chemoselectivity and reliance on precious metal electrodes. In this work, we present a simple solution to this long-standing challenge: Switching the potential waveform from classical direct current to rapid alternating polarity renders various functional groups compatible and enables the reaction on sustainable carbon-based electrodes (amorphous carbon). This breakthrough enabled access to valuable molecules that range from useful unnatural amino acids to promising polymer building blocks from readily available carboxylic acids, including biomass-derived acids. Preliminary mechanistic studies implicate the role of waveform in modulating the local pH around the electrodes and the crucial role of acetone as an unconventional reaction solvent for Kolbe reaction.