Nie Lei, Yang Jiayi, Liu Zhao, Zhou Shibo, Chen Suming, Qi Xiaotian, Lei Aiwen, Yi Hong
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, Hubei, P. R. China.
The Institute for Advanced Studies (IAS), Wuhan University, Wuhan 430072, Hubei, P. R. China.
J Am Chem Soc. 2024 Nov 13;146(45):31330-31338. doi: 10.1021/jacs.4c12925. Epub 2024 Oct 31.
Electrosynthesis has emerged as a versatile and sustainable tool in organic chemistry, offering an efficient pathway for the construction of complex molecular architectures under mild and environmentally benign conditions. Traditional electrochemical approaches, however, predominantly rely on either anodic oxidation or cathodic reduction, limiting their capacity to achieve redox-neutral transformations using a single electrode. In this work, we introduce a linear paired electrolysis strategy that circumvents these limitations, enabling a redox-neutral (3 + 2) annulation of benzofuran with vinyldiazo compounds. This method facilitates the formation of benzofuran-fused tricyclic scaffolds, which are valuable in synthetic chemistry and medicinal applications. The transformation proceeds through sequential anodic oxidation and cathodic reduction, leveraging a radical cation pathway to deliver polycyclic compounds with high selectivity. The efficiency and mechanism of this process are thoroughly validated using cyclic voltammetry and electrochemical mass spectrometry (EC-MS) and supported by theoretical calculations, shedding light on the potential of redox-neutral electrochemical transformations.
电合成已成为有机化学中一种通用且可持续的工具，为在温和且环境友好的条件下构建复杂分子结构提供了一条有效途径。然而，传统的电化学方法主要依赖于阳极氧化或阴极还原，限制了它们使用单个电极实现氧化还原中性转化的能力。在这项工作中，我们引入了一种线性配对电解策略，该策略克服了这些限制，实现了苯并呋喃与乙烯基重氮化合物的氧化还原中性（3 + 2）环化反应。这种方法有助于形成苯并呋喃稠合的三环支架，这些支架在合成化学和药物应用中具有重要价值。该转化过程通过顺序阳极氧化和阴极还原进行，利用自由基阳离子途径以高选择性提供多环化合物。使用循环伏安法和电化学质谱（EC-MS）对该过程的效率和机理进行了全面验证，并得到了理论计算的支持，揭示了氧化还原中性电化学转化的潜力。
