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在甲酸中,通过 H O 实现木质素模型化合物的无金属催化剂氧化 C-C 键断裂。

Metal Catalyst-Free Oxidative C-C Bond Cleavage of a Lignin Model Compound by H O in Formic acid.

机构信息

Institute of Bioengineering and Nanotechnology, 31 Biopolis Way, The Nanos #07-01, Singapore, 138669, Singapore.

出版信息

ChemSusChem. 2020 Apr 7;13(7):1740-1745. doi: 10.1002/cssc.201903180. Epub 2020 Mar 6.

Abstract

Selective cleavage of the β-O-4 ether bond of lignin to produce aromatics is one of the most important topics for the sustainable production of chemicals from biomass. A simple system has been developed for C -C bond cleavage of a β-O-4 ketone-structured lignin model compound (LMC) by H O in formic acid under metal catalyst-free conditions. By using this simple system, with H O , formic acid, and mineral acid catalyst, over 90 % product yield is achieved in 6 h at room temperature. The reaction proceeds through the classic Baeyer-Villiger oxidation and in situ-generated performic acid serves as the key oxidant. The cleavage of alcoholic LMCs by using the presented method in a two-step process is also demonstrated.

摘要

选择性断裂木质素β-O-4 醚键以生产芳烃是从生物质可持续生产化学品的最重要课题之一。本文在无金属催化剂条件下,在甲酸中利用 H O 开发了一种简单的系统,用于β-O-4 酮结构木质素模型化合物(LMC)的 C -C 键断裂。通过使用该简单系统,在室温下以 H O 、甲酸和矿物酸催化剂反应 6 小时,即可获得超过 90%的产物收率。该反应通过经典的 Baeyer-Villiger 氧化进行,原位生成的过甲酸是关键氧化剂。通过两步法,该方法还可用于醇型 LMC 的断裂。

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