Meyer Tim, Rabeah Jabor, Brückner Angelika, Wu Xiao-Feng
Leibniz-Institut für Katalyse e.V., Universität Rostock, Albert-Einstein-Straße 29a, 18059, Rostock, Germany.
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023, Dalian, Liaoning, P. R. China.
Chemistry. 2021 Mar 26;27(18):5642-5647. doi: 10.1002/chem.202100009. Epub 2021 Mar 1.
The palladium-catalyzed oxidative carbonylation of amines toward the synthesis of oxalamides has been established around 30 years ago and it usually needs the presence of (over)stoichiometric amounts of oxidant. In this work, the first transformation of this type in which the oxidant was replaced by visible light is described. The new approach uses a simple robust Pd complex, which can even be partially recycled. A mechanistic reason is provided and supported by control experiments and EPR studies, showing that Pd was formed and Pd was the active species. Both nitrogen- and the intermediate acyl radical can be detected. Moreover, the formation of hydrogen was confirmed by gas GC.
大约30年前就已确立了钯催化胺的氧化羰基化反应以合成草酰胺，该反应通常需要化学计量（过量）的氧化剂存在。在这项工作中，描述了该类型的首次转化，其中氧化剂被可见光取代。新方法使用一种简单且稳定的钯配合物，该配合物甚至可以部分回收利用。通过对照实验和电子顺磁共振研究提供并支持了一个机理原因，表明形成了钯且钯是活性物种。氮自由基和中间的酰基自由基均可被检测到。此外，通过气相色谱法确认了氢气的生成。
