Potential-tuned selective electrosynthesis of azoxy-, azo-and amino-aromatics over a CoP nanosheet cathode

• 来源期刊: 国家科学评论（英文版）
• 关键词: azoxy- azo-and amino-aromatics electrosynthesis metal phosphides nitroarenes selectivity
• 年，卷（期）: 2020,（2）
• 页码范围: 285-295
• 页数: 11页
• 语种: 英文
• DOI: 10.1093/nsr/nwz146

摘要

Azoxy-,azo-and amino-aromatics are among the most widely used building blo.cks 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.