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非血红素型钌催化的化学和位点选择性 C-H 氧化反应。

Non-Heme-Type Ruthenium Catalyzed Chemo- and Site-Selective C-H Oxidation.

机构信息

Department of Chemistry Graduate School of Science, Kyushu University, 744, Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.

Faculty of Arts and Science, Kyushu University, 744, Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.

出版信息

Chem Asian J. 2020 Mar 16;15(6):762-765. doi: 10.1002/asia.202000134. Epub 2020 Feb 27.

Abstract

Herein, we developed a Ru(II)(BPGA) complex that could be used to catalyze chemo- and site-selective C-H oxidation. The described ruthenium complex was designed by replacing one pyridyl group on tris(2-pyridylmethyl)amine with an electron-donating amide ligand that was critical for promoting this type of reaction. More importantly, higher reactivities and better chemo-, and site-selectivities were observed for reactions using the cis-ruthenium complex rather than the trans-one. This reaction could be used to convert sterically less hindered methyne and/or methylene C-H bonds of a various organic substrates, including natural products, into valuable alcohol or ketone products.

摘要

在此,我们开发了一种 Ru(II)(BPGA) 配合物,可用于催化化学选择性和位点选择性 C-H 氧化。所描述的钌配合物是通过用电子供体酰胺配体取代三(2-吡啶基甲基)胺上的一个吡啶基基团来设计的,这对于促进这种类型的反应至关重要。更重要的是,使用顺式-钌配合物而不是反式-钌配合物观察到反应具有更高的反应活性和更好的化学选择性和位点选择性。该反应可用于将各种有机底物(包括天然产物)中空间位阻较小的亚甲基和/或次甲基 C-H 键转化为有价值的醇或酮产物。

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