Potential-tuned selective electrosynthesis of azoxy-, azo- and amino-aromatics over a CoP nanosheet cathode
Potential-tuned selective electrosynthesis of azoxy-, azo- and amino-aromatics over a CoP nanosheet cathode作者机构：Department of Chemistry Institute of Molecular Plus School of Science Tianjin University Tianjin Key Laboratory of Molecular Optoelectronic Sciences Collaborative Innovation Center of Chemical Science and Engineering
出 版 物：《National Science Review》 (国家科学评论(英文版))
年 卷 期：2020年第7卷第2期
页 面：285-295页
核心收录：
学科分类：081704[工学-应用化学] 07[理学] 070205[理学-凝聚态物理] 08[工学] 0817[工学-化学工程与技术] 080501[工学-材料物理与化学] 070303[理学-有机化学] 0805[工学-材料科学与工程（可授工学、理学学位）] 0703[理学-化学] 0702[理学-物理学]
基 金：supported by the National Natural Science Foundation of China(21871206 and 21422104) the Natural Science Foundation of Tianjin City(17JCJQJC44700)
主 题：azoxy- azo- and amino-aromatics electrosynthesis metal phosphides nitroarenes selectivity
摘 要：Azoxy-, azo-and amino-aromatics are among the most widely used building blocks in materials science pharmaceuticals and synthetic chemistry, but their controllable and green synthesis has not yet been well established. Herein, a facile potential-tuned electrosynthesis of azoxy-, azo-and amino-aromatics via aqueous selective reduction of nitroarene feedstocks over a CoP nanosheet cathode is developed. A series of azoxy-, azo-and amino-compounds with excellent selectivity, good functional group tolerance and high yields are produced by applying different bias input. The synthetically significant and challenging asymmetric azoxy-aromatics can be controllably synthesized in moderate to good yields. The use of water as the hydrogen source makes this strategy remarkably fascinating and promising. In addition, deuterated aromatic amines with a high deuterium content can be readily obtained by using D2O. By pairing with anodic oxidation of aliphatic amines to nitriles, synthetically useful building blocks can be simultaneously produced in a CoP||Ni2P two-electrode electrolyzer. Only 1.25 V is required to achieve a current density of 20 mA cm-2, which is much lower than that of overall water splitting(1.70 V). The paired oxidation and reduction reactions can also be driven using a 1.5 V battery to synthesize nitrile and azoxybenzene with good yields and selectivity, further emphasizing the flexibility and controllability of our method. This work paves the way for a promising approach to the green synthesis of valuable chemicals through potential-controlled electrosynthesis.
同方期刊数据库