College of Chemistry and Molecular Sciences, Institute for Advanced Studies (IAS), Wuhan University, Wuhan, 430072, P.R. China.
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, P.R. China.
Nat Commun. 2019 Feb 7;10(1):639. doi: 10.1038/s41467-019-08414-8.
Oxidative C-H/N-H cross-coupling is one of the most atom-economical methods for the construction of C-N bonds. However, traditional oxidative C-H/N-H cross-coupling either required the use of strong oxidants or high reaction temperature, which makes it difficult to tolerate redox active functional groups. Herein we describe an external chemical oxidant-free electrooxidative C-H/N-H cross-coupling between electron-rich arenes and diarylamine derivatives. Under undivided electrolytic conditions, a series of triarylamine derivatives are produced from electron-rich arenes and diarylamine derivatives with high functional group tolerance. Both of the coupling partners are redox active in oxidative C-H/N-H cross-coupling, which enables high regioselectivity in C-N bond formation. Exclusive para-selectivity is observed for the coupling with anilines.
氧化 C-H/N-H 交叉偶联是构建 C-N 键最原子经济的方法之一。然而，传统的氧化 C-H/N-H 交叉偶联要么需要使用强氧化剂，要么需要高温反应，这使得它难以容忍氧化还原活性官能团。在这里，我们描述了一种在无需外加化学氧化剂的条件下，电子富芳烃和二芳基胺衍生物之间的电氧化 C-H/N-H 交叉偶联。在不分流电解条件下，一系列三芳基胺衍生物可以从电子富芳烃和二芳基胺衍生物高产率地得到，具有很高的官能团容忍度。在氧化 C-H/N-H 交叉偶联中，两个偶联伙伴都是氧化还原活性的，这使得 C-N 键形成具有高区域选择性。与苯胺的偶联观察到了独特的对位选择性。
