Amide Synthesis by Nickel/Photoredox-Catalyzed Direct Carbamoylation of (Hetero)Aryl Bromides
Amide Synthesis by Nickel/Photoredox-Catalyzed Direct Carbamoylation of (Hetero)Aryl Bromides
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DOI：
10.1002/anie.202000224
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发表时间：
2020-02-25
影响因子：
16.6
通讯作者：
Melchiorre, Paolo
中科院分区：
文献类型：
--
作者：
Alandini, Nurtalya;Buzzetti, Luca;Melchiorre, Paolo
在此，我们报告了一种单电子催化合成酰胺的策略，使（杂）芳基溴的直接氨基化成为可能。这种自由基交叉偶联方法是基于镍和光氧化还原催化的结合，在室温下进行，并使用容易获得的二氢吡啶作为氨基甲酰自由基的前体。该方法的温和反应条件使其能够耐受含有敏感官能团的底物，并允许在生物相关的杂环中安装酰胺支架。此外，我们还安装了带有电子贫乏和空间阻碍胺的酰胺官能团，这些官能团很难用经典的脱水缩合方法制备。
Herein, we report a one-electron strategy for catalytic amide synthesis that enables the direct carbamoylation of (hetero)aryl bromides. This radical cross-coupling approach, which is based on the combination of nickel and photoredox catalysis, proceeds at ambient temperature and uses readily available dihydropyridines as precursors of carbamoyl radicals. The method's mild reaction conditions make it tolerant of sensitive-functional-group-containing substrates and allow the installation of an amide scaffold within biologically relevant heterocycles. In addition, we installed amide functionalities bearing electron-poor and sterically hindered amine moieties, which would be difficult to prepare with classical dehydrative condensation methods.