脂肪醛参与的氧化—脱羰自由基串联反应

发布时间：2018-04-08 23:32

本文选题：N-芳基丙烯酰胺　切入点：脂肪醛　出处：《湘潭大学》2017年硕士论文

【摘要】：近年来,通过直接的C-H键活化构建C-C键的策略已然在现代有机合成中发展为一种热潮;其中,利用自由基串联反应构筑多样化的C-C键从而应用于合成诸多生物活性分子,也已成为一种常用、高效、便捷的方法。借助这种方法,前人已经实现了N-芳基丙烯酰胺的烷基化反应,得到功能化的吲哚酮类化合物。对比传统的过渡金属催化N-芳基丙烯酰胺与卤代烷烃的烷基化反应,自由基串联反应避免了底物需要预官能团化、额外添加配体或碱、副产物较多等缺陷。但是之前的研究局限于使用结构对称的环烷烃或者芳烃苄位C(sp3)-H键这两类底物,以解决反应区域选择性的问题。为此,我们希望能够发展一种更加方便、有效的方法,从简单易得的原料作为直链或支链烷基自由基的来源,实现其与N-芳基丙烯酰胺的自由基串联反应。本文主要围绕以下内容展开:首先,综述了有关N-芳基丙烯酰胺自由基串联反应的研究进展和醛氧化脱羰反应的发展现状;其次,我们以过氧化二叔丁基作为自由基引发剂和氧化剂,研究了脂肪醛与N-芳基丙烯酰胺的脱羰串联反应,得到了多取代的吲哚-2-酮类产物。该反应无需金属催化剂以及其他任何添加剂、底物普适性广泛、区域选择性好且收率较高,反应过程中并没有烷基碳链的重排,对此我们也提出了一种非链式自由基加成环化的反应机理;最后,我们以前面的研究为基础,尝试将醛脱羰反应运用于其它更多的串联反应中,研究了苯基丙炔酮和N-苯基苯丙炔酰胺的氧化脱羰串联环化反应,构建了其它类型的C-C键或者环状类化合物。
[Abstract]:In recent years, the strategy of forming C-C bond by direct activation of C-H bond has developed into an upsurge in modern organic synthesis, in which a variety of C-C bonds are constructed by using free radical series reaction to synthesize many bioactive molecules.It has also become a common, efficient and convenient method.With this method, the alkylation of N-aryl acrylamide has been realized and the functionalized indole ketones have been obtained.Compared with the traditional transition metal catalyzed alkylation of N-aryl acrylamide with halogenated hydrocarbons, the series reaction of free radical avoids the defects such as the need of pre-functional group, the addition of ligands or alkaloids, and the increase of by-products.However, previous studies have been limited to the use of symmetric substrates of cycloalkanes or aromatic benzyl C(sp3)-H bonds to solve the problem of regioselectivity.Therefore, we hope to develop a more convenient and effective method to realize the series reaction of N-aryl acrylamide by using simple and easily available raw materials as the source of straight chain or branched alkyl radical.This paper mainly focuses on the following aspects: firstly, the research progress of N-aryl acrylamide radical series reaction and the development status of aldehyde oxidative decarbonylation reaction are reviewed.The decarbonylation of aliphatic aldehydes with N-aryl acrylamide was studied using di-tert-#china_person0# as a radical initiator and oxidant. The polysubstituted indole-2-ketones were obtained.This reaction requires no metal catalyst or any other additives. The substrate is universal, the region selectivity is good and the yield is high. There is no rearrangement of alkyl carbon chain in the reaction process.We also propose a mechanism of addition cyclization of non-chain free radicals. Finally, we try to apply the decarbonylation of aldehydes to other series reactions based on the previous studies.The oxidative decarbonylation of phenylpropargyl ketone and N-phenylphenylpropargyl amide was studied in series, and other C-C bond or cyclic compounds were constructed.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25

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