Imada Yasushi, Okada Yohei, Noguchi Keiichi, Chiba Kazuhiro
Department of Applied Biological Science, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu, Tokyo, 183-8509, Japan.
Department of Chemical Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo, 184-8588, Japan.
Angew Chem Int Ed Engl. 2019 Jan 2;58(1):125-129. doi: 10.1002/anie.201809454. Epub 2018 Nov 27.
Electrode materials can have a significant impact on the course of an electrolysis reaction. Of particular interest is that different electrodes can generate different products from the same substrate. The electrode-material-selective transformations of styrene derivatives with molecular oxygen are reported. Platinum electrodes afford carbonyl products via cleavage of olefins, whereas tetrahydrofuran formation is achieved with carbon electrodes. A variety of different styrenes are available for both reactions. Electrolysis allows straightforward and mild chemical conversions that are metal- and oxidant-free. Electrochemical measurements illuminate the different effects of platinum and carbon electrodes on styrenes. The key to the differing reactions is probably that the oxidation potentials of the substrates are lower (higher HOMO energy) on carbon electrodes than on platinum electrodes. The adsorption of the substrates on carbon electrodes can also promote tetrahydrofuran formation.
电极材料对电解反应的过程会产生重大影响。特别值得关注的是，不同的电极能从同一底物生成不同的产物。本文报道了苯乙烯衍生物与分子氧的电极材料选择性转化反应。铂电极通过烯烃的裂解生成羰基产物，而碳电极则能实现四氢呋喃的生成。两种反应均有多种不同的苯乙烯可供使用。电解反应能实现直接且温和的化学转化，无需使用金属和氧化剂。电化学测量揭示了铂电极和碳电极对苯乙烯的不同影响。不同反应的关键可能在于，底物在碳电极上的氧化电位低于铂电极（更高的HOMO能量）。底物在碳电极上的吸附也能促进四氢呋喃的生成。
