紫罗兰酮多位点选择性氧化反应及乙烯基苯酚氧化去芳香化反应的研究

发布时间：2018-07-17 06:56

【摘要】：在天然产物的合成研究中,有许多中间体需要通过氧化反应来获得,例如：在合成植物激素脱落酸的过程中,紫罗兰酮的选择性环氧化在合成脱落酸过程中有着关键的作用。另外,吲哚与吲哚嗪是天然产物以及药物合成中普遍存在的骨架结构,通过氧化去芳香化这一特殊氧化手段,快速构建这一类骨架在药物合成中具有非常重要的意义。1.本论文通过合成并筛选了一系列不同位阻、不同电性的有机硒催化剂,实现选择性地催化氧化紫罗兰酮的不同位点,以72%的收率选择性地得到紫罗兰酮的环氧化产物,为后续高效合成脱落酸提供了方法学保证,该方法催化剂可以循环使用,是一种潜在的环境友好的合成脱落酸关键中间体的方法。2.探索高价碘催化乙烯基苯酚的氧化去芳香化反应,以此来快速构建吲哚与吲哚嗪的骨架结构,该方法未使用任何过渡金属催化剂,本文共合成了30该类衍生物,收率最高可达%,dr值最高达20：1。利用该方法可高效地构建一类吲哚与吲哚嗪的骨架结构。3.以高价碘催化乙烯基苯酚氧化去芳香化的反应为基础,实现了一些生物碱类似骨架的修饰与转化,产生了6种不同的化合物。所有目标产物结构均通过IR、1H-NMR、13C-NMR、GC-MS进行了表征。
[Abstract]:In the study of the synthesis of natural products, many intermediates need to be obtained by oxidation. For example, the selective epoxidation of ionone plays a key role in the synthesis of abscisic acid in the process of synthesizing plant hormone abscisic acid. In addition, indole and indole are the natural products and the skeleton structure in drug synthesis. It is very important to construct this kind of skeleton rapidly in the synthesis of drugs by oxidation and aromatization as a special oxidation method. In this paper, a series of organic selenium catalysts with different steric hindrance and different electrical properties were synthesized and selected to selectively catalyze the oxidation of ionone at different sites. The epoxidation products of ionone were selectively obtained in 72% yield. This method provides a methodological guarantee for the subsequent efficient synthesis of abscisic acid. The catalyst can be recycled and is a potential environmentally friendly method for the synthesis of key intermediates of abscisic acid. In order to rapidly construct the skeleton structure of indole and indole, 30 derivatives were synthesized without any transition metal catalyst by exploring the oxidation and aromatization of vinylphenol catalyzed by high valence iodine, so as to construct the skeleton structure of indole and indole rapidly. The highest yield can be as high as 20: 1. By using this method, the skeleton structure of a class of indole and indole can be constructed efficiently. Based on the dearomatization of vinyl phenol catalyzed by high valence iodine, some alkaloid analogous cytoskeletons were modified and transformed into six different compounds. The structure of all the target products was characterized by IR 1H-NMR-13C-NMR-GC-MS.
【学位授予单位】：扬州大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

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