Bera Subhankar, Sen Subhabrata, Maiti Debajit
Department of Chemistry, School of Natural Sciences, Shiv Nadar IoE Deemed to be University, Delhi-NCR Dadri, Chithera, Gautam Buddha Nagar, Uttar Pradesh 201314, India.
J Am Chem Soc. 2024 Sep 11;146(36):25166-25175. doi: 10.1021/jacs.4c08826. Epub 2024 Aug 28.
Electro-photochemical organic synthesis is a rapidly growing field. Recently, technological advancement has contributed significantly to improve electro- and photolytic organic transformations in terms of energy efficiency and productivity. Herein, we have introduced alternating electrode electrolysis|alternate electrode electrolysis (AEE), a new technique in electrosynthesis which in combination with blue LED demonstrated an interesting three-component reaction with aryl diazoesters, 1,4-quinones, and acetone to synthesize ketal-functionalized 1,4-quinones. The AEE setup consists of two pairs of cathode-anode compared to the conventional setup of one pair. Each pair would be polarized or in a resting stage with a preset interval of choice. This would maintain a continuous potential resulting in maximum current and would facilitate the mass transport, thereby increasing the overall efficiency of the reaction. AEE offers the efficient utilization of photochemically generated carbenes. We extended AEE applications in paired photoelectrolysis reactions for the late-stage functionalization of bioactive molecules and pharmaceutical agents. As an application of AEE in electrosynthesis (without light), we demonstrated the efficient hydroxylation of fluorinated benzene and the reduction of benzonitrile to benzyl amine. The amalgamation of AEE with blue LED contributes to sustainability, and we believe that it holds great promise in the field of electro-photochemical organic synthesis.
电光化学有机合成是一个快速发展的领域。最近，技术进步在能源效率和生产率方面对改善电催化和光解有机转化做出了重大贡献。在此，我们介绍了交替电极电解（AEE），这是一种电合成新技术，它与蓝色发光二极管相结合，展示了与芳基重氮酯、1,4-醌和丙酮发生的有趣的三组分反应，以合成缩酮官能化的1,4-醌。与传统的一对阴极-阳极装置相比，AEE装置由两对阴极-阳极组成。每对电极将以预设的选择间隔极化或处于静止阶段。这将维持连续的电位，从而产生最大电流，并将促进传质，从而提高反应的整体效率。AEE能有效利用光化学产生的卡宾。我们将AEE应用扩展到用于生物活性分子和药物后期功能化的成对光电解反应中。作为AEE在电合成（无光）中的应用，我们展示了氟化苯的高效羟基化反应以及苯甲腈还原为苄胺的反应。AEE与蓝色发光二极管的结合有助于实现可持续性，我们相信它在电光化学有机合成领域具有巨大的潜力。
