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在温和条件下使用铜-氧化锰作为可重复使用的催化剂,实现芳烃和杂芳烃与酰胺及胺的C-H酰胺化和胺化反应。

C-H Amidation and Amination of Arenes and Heteroarenes with Amide and Amine using Cu-MnO as a Reusable Catalyst under Mild Conditions.

作者信息

Singh Harshvardhan, Sen Chiranjit, Suresh Eringathodi, Panda Asit B, Ghosh Subhash C

机构信息

Central Salt and Marine Chemicals Research Institute (CSIR-CSMCRI), Bhavnagar, Gujarat 364002, India.

Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, Uttar Pradesh 201002, India.

出版信息

J Org Chem. 2021 Feb 19;86(4):3261-3275. doi: 10.1021/acs.joc.0c02603. Epub 2021 Feb 1.

Abstract

An atom-economical and efficient route for the direct amidation and amination of aryl C-H bonds using our synthesized recyclable heterogeneous Cu-MnO catalyst is reported here. The direct C-H amidation was carried out using a simple amide without any preactivated coupling partner, and simple air was used as the sole oxidant. The reaction proceeds very smoothly with a broad range of substrates containing numerous functional groups in very good to excellent yields. Direct C-H aminations with a secondary amine were carried out under base-, ligand-, and external oxidant-free conditions in very good to excellent yields in very mild conditions. Both the amidation and amination can be scaled up on a gram scale with similar yields. The major advantage is that our catalyst is recyclable and reused several times without any significant loss of reactivity.

摘要

本文报道了一种原子经济且高效的路线,该路线使用我们合成的可循环使用的多相铜 - 氧化锰催化剂,实现芳基碳氢键的直接酰胺化和胺化反应。直接碳氢键酰胺化反应使用一种简单的酰胺,无需任何预活化的偶联试剂,仅使用简单的空气作为唯一的氧化剂。该反应能非常顺利地进行,对于含有众多官能团的各种底物,产率非常高,可达良好至优异水平。与仲胺的直接碳氢键胺化反应在无碱、无配体和无外部氧化剂的条件下进行,在非常温和的条件下产率也非常高,可达良好至优异水平。酰胺化和胺化反应均可放大至克级规模,且产率相似。主要优点是我们的催化剂可循环使用,能重复使用多次且反应活性无明显损失。

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