基于钯和降冰片烯共催化构建邻氨基苯乙酮类化合物的研究

发布时间：2018-05-03 05:28

本文选题：羰基化合物 + Heck反应　；参考：《中国科学技术大学》2017年硕士论文

【摘要】：Catellani反应是钯催化,降冰片烯介导的多米诺偶联反应,这个反应可以一步合成多取代的芳香化合物,在天然产物及药物合成中具有重要意义,因而受到广泛关注。自1997年Catellani反应首次报道以来,越来越多的亲电试剂及淬灭试剂被发现,各种不同结构的化合物被合成。酮作为一种重要的有机官能团,其高效合成具有重要的研究意义。目前,芳基酮的合成方法已有多篇文献报道,本论文以烯醚作为淬灭试剂应用到Catellani反应中,发展了一种新的合成芳基酮的方法。论文第一部分介绍了 Catellani反应的研究进展。以不同的淬灭试剂终止反应为思路,简述了 Heck 偶联、Suzuki 偶联、Buchwald-Hartwig 偶联、Sonogashira偶联、直接C-H芳基化、还原淬灭等方式终止的Catellani反应,也介绍了近几年发展的钯/降冰片烯催化,导向基团诱导的间位C-H活化反应以及Catellani反应在天然产物全合成中的应用。论文第二部分研究了以吗啡啉类的氮氧化物作为亲电试剂(BzONR1R2),以苄基乙烯基醚作为淬灭试剂,碳酸铯为碱,在钯/降冰片烯作用下,实现了芳基碘化物邻位胺化,本位乙烯基醚化,一步合成苄氧基乙烯基芳烃化合物。该反应条件温和,操作简单,并且具有很好的区域选择性和底物普适性。此外,苄氧基乙烯基醚在酸性条件下可以很容易的转化为邻氨基苯乙酮类化合物,这为制备邻氨基苯乙酮提供了一种简便的方法。通过对苄氧基乙烯基芳烃和邻氨基苯乙酮的简单探索,发现它们可以发生一系列衍生化反应,在医药、材料科学等领域具有潜在的应用价值。
[Abstract]:Catellani reaction is a palladium catalyzed domino coupling reaction mediated by norbornene. It can be used to synthesize polysubstituted aromatic compounds in one step, which is of great significance in the synthesis of natural products and drugs. Since the Catellani reaction was first reported in 1997, more and more electrophilic and quenched reagents have been found, and various compounds with different structures have been synthesized. Ketone as an important organic functional group, its high-efficiency synthesis has important significance. At present, the synthesis of aryl ketones has been reported in many literatures. In this paper, a new method of synthesis of aryl ketones has been developed by using enyl ether as quenching reagent in Catellani reaction. In the first part of this paper, the research progress of Catellani reaction is introduced. Based on the different quench reagent termination reactions, the Catellani reaction terminated by Heck coupling, direct C-H arylation, reduction quenching and so on are briefly described. The palladium / norbornene catalysis developed in recent years is also introduced. M-C-H activation induced by guided group and application of Catellani reaction in the total synthesis of natural products. In the second part of the thesis, the aryl iodide o-amination of aryl iodide was studied by using morphine nitrogen oxides as electrophilic reagent, benzyl vinyl ether as quenching reagent, cesium carbonate as base, and PD / norbornene as base. Benzoxy vinyl aromatic compounds were synthesized by one step etherification based on vinyl group. The reaction conditions are mild, simple, and have good regional selectivity and substrate universality. In addition, benzoxy vinyl ether can be easily converted into o-aminophenone compounds under acidic conditions, which provides a simple method for the preparation of o-aminoacetophenone. Through the simple exploration of benzoxy vinyl aromatics and o-aminoacetophenone, it is found that they can undergo a series of derivatization reactions, which have potential application value in medicine, material science and other fields.
【学位授予单位】：中国科学技术大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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