Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education and Yunnan Province, School of Chemical Science and Technology, Yunnan University, Kunming 650091, P.R. China.
Org Lett. 2020 Aug 21;22(16):6547-6551. doi: 10.1021/acs.orglett.0c02320. Epub 2020 Aug 11.
Herein, we describe a Cu-catalyzed approach to directly accessing aromatic heterocyclic amines from cyclic amides. The most-reported methods for cyclic amide conversions to aromatic heterocyclic amines use an activating group, such as a halogen atom or a trifluoromethane sulfonyl group. However, subsequent elimination of activating groups during the amination process results in significant waste. This copper-catalyzed direct amination of cyclic amides in DMF forms aromatic heterocyclic amines with environmental friendliness and readily available reagents. A plausible radical mechanism has been proposed for the reaction. Meanwhile, the coordinating effect of the atom is key to the success of this reaction, which provides assistance to the copper ions for the activation and amination of C-O bonds.
在这里，我们描述了一种铜催化的方法，可直接从环状酰胺中获得芳族杂环胺。最常报道的将环状酰胺转化为芳族杂环胺的方法使用活化基团，例如卤素原子或三氟甲磺酸酯基。然而，在胺化过程中去除活化基团会导致大量浪费。这种铜催化的 DMF 中环状酰胺的直接胺化反应以环境友好和易得的试剂形成芳族杂环胺。提出了一种合理的自由基反应机理。同时， 原子的配位效应是该反应成功的关键，它为铜离子提供了对 C-O 键的活化和胺化的帮助。
