氧化脱氢芳构化反应在吡咯和中氮茚合成中的应用

发布时间：2018-04-04 03:39

本文选题：吡咯　切入点：中氮茚　出处：《西南科技大学》2017年硕士论文

【摘要】：含氮杂环化合物广泛存在于天然产物结构单元中,大多数具有很好的潜在生物活性,广泛应用于生物、医药、农药及材料等领域。关于含氮杂环化合物的合成方法和生物活性研究一直受到化学家及生物学家的广泛关注。其中,吡咯和中氮茚是两类重要的芳香含氮杂环化合物。近年来,氧化脱氢芳构化反应在有机合成领域的应用取得了很大的发展。与其它合成方法相比较,脱氢芳构化反应具有很好的原子经济性,是当代有机合成领域的研究热点之一。而有机氧化剂促进的反应具有环境友好、收率高和条件温和等优点,通常无需苛刻的无水无氧条件。本文主要研究了利用有机氧化剂促进的脱氢芳构化反应,从简单原料出发,利用一锅法,高效地合成了一系列多取代吡咯衍生物和3-芳基/3-烷基中氮茚衍生物。研究内容主要包含以下三个方面:第一,多取代吡咯的合成。以过氧化二苯甲酰为氧化剂,实现了四氢吡咯衍生物的脱氢芳构化反应,得到吡咯化合物。最终实现将银催化亚胺与缺电子烯烃之间的1,3-偶极环加成反应和氧化脱氢芳构化反应串联,通过一锅法合成一系列多取代吡咯化合物,产率最高达89%。同时,将该反应成功地扩大至克量级,并通过动力学控制实验研究,推测出了该条件下其脱氢芳构化过程可能的机理。第二,3-芳基中氮茚的合成。以2,2,6,6-四甲基哌啶氮氧(TEMPO)为氧化剂,实现了以吡啶、卤化苄和烯烃为原料,通过一锅法合成了一系列3-芳基中氮茚衍生物,产率最高达100%,并将该反应成功地放大至克量级。第三,3-烷基中氮茚的合成。在3-芳基中氮茚的合成研究基础上,同样以TEMPO为氧化剂,实现了以吡啶、卤代烷烃和烯烃为原料,通过一锅法合成了一系列3-烷基中氮茚衍生物,产率最高达97%。
[Abstract]:Nitrogen-containing heterocyclic compounds are widely used in the structural units of natural products, most of which have good potential biological activity and are widely used in biology, medicine, pesticides and materials.The synthesis and bioactivity of nitrogen-containing heterocyclic compounds have been widely concerned by chemists and biologists.Pyrrole and indolizine are two important aromatic aromatic heterocyclic compounds.In recent years, the application of oxidative dehydrogenation aromatization in the field of organic synthesis has been greatly developed.Compared with other synthesis methods, dehydroaromatization has a good atomic economy and is one of the research hotspots in the field of organic synthesis.However, the reaction promoted by organic oxidants has the advantages of environmental friendliness, high yield and mild conditions, which usually do not require harsh anhydrous and anaerobic conditions.In this paper, a series of polysubstituted pyrrole derivatives and 3-aryl / 3-alkyl derivatives were synthesized from simple raw materials and one-pot method by dehydroaromatization promoted by organic oxidants.The research mainly includes the following three aspects: first, the synthesis of polysubstituted pyrrole.The dehydroaromatization of tetrahydropyrrole derivatives was carried out by using dibenzoyl peroxide as oxidant to obtain pyrrole compounds.Finally, a series of polysubstituted pyrrole compounds were synthesized by one-pot method in series of silver catalyzed 1 ~ 3- dipolar cycloaddition reaction and oxidative dehydrogenation aromatization between imine and electron deficient olefin. The yield was up to 89%.At the same time, the reaction was successfully extended to the order of g, and the possible mechanism of the dehydroaromatization was deduced by the kinetic control experiments.Synthesis of indolizine in the second 3-aryl group.A series of 3-aryl derivatives were synthesized from pyridine, benzyl halide and olefin by one-pot method using 2 ~ (2 +) ~ (2 +) ~ (2 +) ~ (2 +) ~ (2 +) -tetramethylpiperidinazo (TEMPO) as oxidant. The yield was up to 100%, and the reaction was successfully amplified to g ~ (-1).Synthesis of indolizine in the third 3-alkyl.Based on the synthesis of 3-aryl indolizine and TEMPO as oxidant, a series of 3-alkyl indolizine derivatives were synthesized by one-pot method using pyridine, halogenated hydrocarbons and olefins as raw materials, with the highest yield of 9775.
【学位授予单位】：西南科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626

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