无金属电化学氧化烯烃酰胺的二氟乙基化/环化反应构建二氟乙基化氮杂环化合物

Metal-Free Electrochemical Oxidative Difluoroethylation/Cyclization of Olefinic Amides To Construct Difluoroethylated Azaheterocycles.

作者信息

Tian Yunfei, Zheng Luping, Wang Zhiqiang, Li Zejiang, Fu Weijun

机构信息

College of Chemistry and Chemical Engineering, Key Laboratory of Fuction-Oriented Porous Materials of Henan Province, Luoyang Normal University, Luoyang, Henan 471934, P. R. China.

Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, College of Chemistry and Materials Science, Key Laboratory of Chemical Biology of Hebei Province, Hebei University, Baoding, Hebei 071002, P. R. China.

出版信息

J Org Chem. 2023 Feb 3;88(3):1875-1883. doi: 10.1021/acs.joc.2c02579. Epub 2023 Jan 20.

DOI:10.1021/acs.joc.2c02579

PMID:36669162

Abstract

A new strategy of electrochemical oxidative difluoroethylation to generate difluoroethyl radical with sodium difluoroethylsulfinate (DFES-Na) has been reported for the first time. The method allows quick access to a variety of valuable difluoroethylated azaheterocycles including oxindoles and isoquinoline-1,3-diones via radical tandem difluoroethylation/cyclization in moderate to good yields. The electrochemical cyclopropyldifluoromethylation of -arylacrylamides also works well using this strategy. Moreover, radical capture and cyclic voltammetry (CV) experiments are also carried out to determine the proposed mechanism.

摘要

首次报道了一种用电化学氧化二氟乙基化反应，以二氟乙基亚磺酸钠（DFES-Na）生成二氟乙基自由基的新策略。该方法能够通过自由基串联二氟乙基化/环化反应，以中等至良好的产率快速获得各种有价值的二氟乙基化氮杂环化合物，包括氧化吲哚和异喹啉-1,3-二酮。使用该策略，-芳基丙烯酰胺的电化学环丙基二氟甲基化反应也能顺利进行。此外，还进行了自由基捕获和循环伏安法（CV）实验以确定所提出的反应机理。