2,2,6,6-四甲基哌啶-1-氧自由基在醇氧化研究中的应用

Application of TEMPO in the catalytic alcohol oxidation

2,2,6,6-四甲基哌啶-1-氧自由基(TEMPO)作为有机小分子,形成的催化醇氧化反应体系相对传统醇氧化具有高效性、高选择性、反应条件温和等优点,可以解决传统醇氧化工艺中反应条件苛刻、成本高以及产生大量污染物的问题,是目前最具前景的醇氧化技术之一。本文综述了近年来关于TEMPO体系在催化醇氧化方面的相关研究进展,重点介绍了均相环境下过渡金属(铜、铁、钌等)参与和无过渡金属参与的TEMPO催化醇氧化,以及多相环境下的固载型TEMPO催化醇氧化,并根据催化反应效率、氧化成本、实际应用性等因素比较总结了均相催化和非均相催化两种类型催化氧化体系的优缺点。指出离子液体与TEMPO的耦合体系、廉价过渡金属掺杂的TEMPO体系和高稳定性碳基材料负载型TEMPO体系是该类型催化剂优化调控的目标与方向。

As a small organic molecule,TEMPO(2,2,6,6-tetramethylpiperidine-1-oxyl radical)forms a catalytic alcohol oxidation reaction system with high efficiency,high selectivity and mild reaction conditions.It can solve the problems of harsh reaction conditions,high cost and large amount of pollutants in the traditional alcohol oxidation process,and therefore becomes one of the most promising alcohol oxidation technologies at present.This article reviews the research progress of TEMPO involved catalytic alcohol oxidation in recent years,focusing on the homogeneous TEMPO catalytic alcohol oxidation with and without transition metals,as well as the solid-supported heterogeneous TEMPO catalytic alcohol oxidation,and then compares the advantages and disadvantages of homogeneous and heterogeneous catalysis,from the aspects of catalytic reaction efficiency,oxidation cost,practical applicability and other factors.In addition,it is pointed out that the establishments of ionic liquid-TEMPO coupling system,lowcost transition metal-doped TEMPO system,and high-stability carbon-based material-supported TEMPO system are the goals and directions for optimal regulation of this type of catalyst.