光—铜双催化的肉桂酸脱羧二氟乙酰基化研究

发布时间：2018-10-30 15:13

【摘要】：以二氟烷基化为代表的含氟基团因其独特的生物学活性和化学特性在新型材料和创新药物研究方面受到了来自工业界及学术界广泛的关注,但有机合成中引入二氟取代基团的经典方法存在条件苛刻,试剂昂贵,环境友好性较差等缺点。因而寻求一种操作简便,反应效率高,绿色环保的新型合成方法就显得十分必要。本论文主要对可见光-过渡金属双催化体系下,以碘二氟乙酸乙酯为氟源,肉桂酸的脱羧偶联反应进行研究。全文共分为三大部分:第一章概述了引入二氟取代基团反应的反应类型以及相关机理,着重介绍了通过sp2杂化碳原子的官能团化合成二氟甲基衍生物的研究进展,并总结了新型合成方法的应用。第二章简单介绍了可见光催化及可见光参与的双催化体系的研究近况及发展前景,并对其在有机合成方法学中的应用及机理研究进行了介绍。第三章主要介绍了我们发展的一种可见光-过渡金属双催化的肉桂酸和碘二氟乙酸乙酯的脱羧偶联反应。研究了在常温下进行,以二氯甲烷为溶剂,加入2倍量的三乙胺,搅拌反应12小时,底物通过可见光催化剂引发,通过可见光催化剂与过渡金属催化剂组成的双催化剂体系的催化,生成了一系列的α,β-不饱和二氟乙酰基取代物。同时,我们对底物的适用性进行了研究并通过对机理的相关验证实验,提出了合理的反应机理。产物的结构通过1H NMR,13C NMR等测试手段进行了确定。本论文重点是区别于传统的引入二氟取代基的方法,对可见光-过渡金属双催化的脱羧偶联反应进行了研究,此方法简洁,环保并高效。
[Abstract]:Fluorine-containing groups, represented by difluoroalkylation, have attracted extensive attention from industry and academia for their unique biological activity and chemical properties in the research of new materials and innovative drugs. However, the classical method of introducing difluoro substituents into organic synthesis has some disadvantages, such as harsh conditions, expensive reagents and poor environmental friendliness. Therefore, it is necessary to seek a new synthetic method with simple operation, high reaction efficiency and environmental protection. In this paper, the decarboxylation of cinnamic acid with ethyl iodifluoroacetate as fluorine source was studied in the system of visible light and transition metal double catalysis. The thesis is divided into three parts: the first chapter summarizes the reaction types and related mechanisms of the introduction of difluoro substituted groups, and emphatically introduces the research progress in the synthesis of difluoromethyl derivatives by the functionalization of sp2 hybrid carbon atoms. The application of new synthesis method is summarized. In the second chapter, the research status and development prospect of visible light catalysis and visible light double catalysis system are briefly introduced, and the application and mechanism of the system in organic synthesis methodology are also introduced. In chapter 3, we mainly introduce a visible light-transition metal double-catalyzed decarboxylation of cinnamic acid and ethyl iodifluoroacetate. The reaction was carried out at room temperature with dichloromethane as solvent, triethylamine was added 2 times, stirring for 12 hours, and the substrate was initiated by visible light catalyst. A series of 伪, 尾 -unsaturated difluoroacetyl substituents were synthesized by the double catalyst system composed of visible light catalyst and transition metal catalyst. At the same time, we studied the applicability of the substrate and put forward a reasonable reaction mechanism through the relevant verification experiments of the mechanism. The structure of the product was determined by 1H NMR,13C NMR. The emphasis of this paper is to study the decarboxylation coupling reaction catalyzed by visible light and transition metal, which is simple, environmentally friendly and efficient, which is different from the traditional method of introducing difluorinated substituents.
【学位授予单位】：兰州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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