Palladium-catalysed oxidative carbonylation using oxygen as the oxidant is an economical approach; however, the gas mixture of CO and air has an explosive limit of 12.5–74.0% that could hamper extensive application of this process. Herein we report an electrochemical aminocarbonylation of alkynes under atmospheric pressure in an undivided cell without an external oxidant. The transformation has a broad substrate scope (83 examples) that involves primary amines and ammonium salts. Furthermore, mechanistic studies through cyclic voltammetry, in situ infrared and quick-scanning X-ray absorption fine structure spectroscopy reveal the reasons for this protocol proceeding smoothly under electrochemical conditions.

使用氧气作为氧化剂的钯催化的氧化羰基化是一种经济的方法。但是，一氧化碳和空气的混合气体爆炸极限为12.5–74.0％，这可能会阻碍该工艺的广泛应用。在本文中，我们报道了在没有外部氧化剂的情况下，在未分开的电池中，大气压下炔烃的电化学氨基羰基化反应。该转化具有广泛的底物范围（83个实例），涉及伯胺和铵盐。此外，通过循环伏安法，原位红外和快速扫描X射线吸收精细结构光谱的机理研究揭示了该方案在电化学条件下顺利进行的原因。