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钌催化叔膦的C-H键烷基化和二氟甲基化反应

C-H Bond Alkylations and Difluoromethylation of Tertiary Phosphines Using a Ruthenium Catalyst.

作者信息

Li Gang, An Jiangzhen, Jia Chunqi, Yan Bingxu, Zhong Lei, Wang Junjie, Yang Suling

机构信息

College of Chemistry and Chemical Engineering, Henan Province Key Laboratory of New Optoelectronic Functional Materials, Anyang Normal University, Anyang 455002, P. R. China.

Engineering Research Center of Molecular Medicine of Ministry of Education, Key Laboratory of Fujian Molecular Medicine, Key Laboratory of Xiamen Marine and Gene Drugs, School of Biomedical Sciences, Huaqiao University, Xiamen 361021, P. R. China.

出版信息

Org Lett. 2020 Dec 18;22(24):9450-9455. doi: 10.1021/acs.orglett.0c03377. Epub 2020 Nov 24.

Abstract

-C-H bond functionalization of tertiary phosphines was developed using [Ru(-cymene)Cl] as a catalyst. Desired product structures were confirmed by single-crystal X-ray diffraction. Mechanistic experiments indicated that -C-H bond functionalization was a radical reaction and that a hexagonal ruthenacycle complex was a crucial intermediate in the process. Therefore, this study provides a novel method for the late-stage -position modification of biphenyl monophosphine ligands.

摘要

以[Ru(对异丙基苯)Cl]为催化剂实现了叔膦的-C-H键官能化。通过单晶X射线衍射确定了所需产物的结构。机理实验表明,-C-H键官能化是一个自由基反应,并且六元钌环配合物是该过程中的关键中间体。因此,本研究为联苯单膦配体的后期 - 位修饰提供了一种新方法。

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