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镍/光氧化还原催化(杂)芳基溴化物的直接氨甲酰化反应合成酰胺。

Amide Synthesis by Nickel/Photoredox-Catalyzed Direct Carbamoylation of (Hetero)Aryl Bromides.

机构信息

ICIQ - Institute of Chemical Research of Catalonia the Barcelona Institute of Science and Technology, Avenida Països Catalans 16, 43007, Tarragona, Spain.

Department of Biomolecular Sciences, University of Urbino "Carlo Bo", via I. Maggetti 24, 61029, Urbino, Italy.

出版信息

Angew Chem Int Ed Engl. 2020 Mar 23;59(13):5248-5253. doi: 10.1002/anie.202000224. Epub 2020 Feb 25.

Abstract

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.

摘要

在此,我们报告了一种用于催化酰胺合成的单电子策略,该策略能够实现(杂)芳基溴化物的直接氨甲酰化。这种基于镍和光氧化还原催化结合的自由基交叉偶联方法在室温下进行,并且使用易得的二氢吡啶作为氨甲酰自由基的前体。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,我们还安装了带有缺电子和空间位阻胺部分的酰胺官能团,这些官能团用经典的脱水缩合方法很难制备。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/242a/7155093/52b259b82019/ANIE-59-5248-g001.jpg

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