Overcoming the limitations of Kolbe coupling with waveform-controlled electrosynthesis
Overcoming the limitations of Kolbe coupling with waveform-controlled electrosynthesis
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DOI：
10.1126/science.adf4762
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发表时间：
2023-04-07
期刊：
影响因子：
56.9
通讯作者：
Baran，Phil S.
中科院分区：
文献类型：
--
作者：
Hioki，Yuta;Costantini，Matteo;Baran，Phil S.
柯尔贝反应通过电化学脱羧偶联形成碳-碳键。尽管经过了世纪的研究，但由于极差的化学选择性和对贵金属电极的依赖，该反应的应用有限。在这项工作中，我们提出了一个简单的解决方案来解决这个长期存在的挑战：将电位波形从经典的直流电切换到快速的交变极性，使各种官能团相容，并使反应能够在可持续的碳基电极（无定形碳）上进行。这一突破使人们能够获得有价值的分子，从有用的非天然氨基酸到来自容易获得的羧酸（包括生物质衍生的酸）的有前途的聚合物构建块。初步的机理研究暗示了波形在调节电极周围的局部pH值中的作用，以及丙酮作为Kolbe反应的非常规反应溶剂的关键作用。
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.