基于碘催化杂环氮氧化物C-H键的直接烯基化反应研究

发布时间：2018-03-02 04:15

本文关键词： C-H键活化无金属乙烯基喹啉碘催化　出处：《郑州大学》2017年硕士论文　论文类型：学位论文

【摘要】：C-H键活化反应作为一种高效、直接构建C-X(X=C,N,P,S,O等)键的方法,在有机合成、生物制药和功能性材料等领域吸引了科学家们的普遍关注。在探索直接C-H键活化的过程中,我们发现以N-O基团作为氧化定位基团的方法具有区域选择性好、反应活性高的优点。此外,喹啉作为含氮杂环类化合物中重要的一员,已经被广泛应用于医药、功能材料和染料工业中。因此,以N-O基团作为氧化导向定位基团,通过直接C-H键活化的方法,得到喹啉化合物官能团化产物的合成策略引起了我们的关注。乙烯基喹啉类化合物具有独特的光学性能和生物活性,广泛存在于天然产物、功能性材料和药物分子之中。目前通过直接C-H键活化实现喹啉类化合物烯基化反应的合成策略主要集中于过渡金属催化和微波反应。然而,这些反应方法通常条件苛刻,需要使用比较昂贵的过渡金属和过量的氧化剂,反应条件难以控制。因此如何开发简单高效、原子经济的方法来合成乙烯基喹啉类化合物是一个挑战。基于此,本论文主要研究了基于碘催化杂环氮氧化物C-H键的直接烯基化反应,我们开发出一种简单、高效的方法来合成一系列乙烯基喹啉类化合物。该方案是以喹啉氮氧化物和苯乙烯为底物,碘单质作为催化剂,在无外加金属和氧化剂的条件下,以高达96%的收率合成了一系列烯基化的含氮杂环类化合物(Scheme 1)。该方法使用了低毒和后处理简单的分子碘作为催化剂,操作简单、对环境污染小,同时还具有区域选择性好、催化效率高、原子经济性好、能适用于放大生产等优点。经过考察已报道的文献和一系列的对照实验,推测该烯基化反应的机理如下图所示(Scheme 2)：
[Abstract]:C-H bond activation reaction, as an efficient and direct method to construct C-XTX (CNN) PNN PNNPNPNPNPNSZO) bonds, has attracted widespread attention of scientists in the fields of organic synthesis, biopharmaceutical and functional materials, etc. In the process of exploring the activation of direct C-H bonds, the activation of C-H bonds has attracted a lot of attention from scientists. We found that N-O group as oxidation group has the advantages of good regioselectivity and high reaction activity. In addition, quinoline, as an important member of nitrogen-containing heterocyclic compounds, has been widely used in medicine. In functional materials and dye industries, therefore, N-O groups are used as oxidation-oriented orientation groups, which are activated by direct C-H bonds. The synthesis strategy of functional quinoline compounds has attracted our attention. Vinyl quinoline compounds have unique optical properties and biological activities and are widely used in natural products. Among functional materials and drug molecules, the current synthesis strategies for the alkylation of quinoline compounds by direct C-H bond activation are mainly focused on transition metal catalysis and microwave reactions. It is difficult to control the reaction conditions that require the use of more expensive transition metals and excess oxidants. Therefore, how to develop a simple, efficient, atomic and economical method for the synthesis of vinyl quinoline compounds is a challenge. In this paper, the direct alkylation of heterocyclic nitrogen oxide C-H bond catalyzed by iodine was studied. A series of vinyl quinoline compounds were synthesized by using quinoline nitrogen oxides and styrene as substrates, iodine as catalyst, and without addition of metal and oxidant. A series of nitrogen-containing heterocyclic compounds were synthesized in a yield of up to 96%. In this method, low toxicity and simple reprocessing molecular iodine were used as catalysts, the operation was simple, the environmental pollution was small, and the region selectivity was good. The catalytic efficiency is high, the atom economy is good, and it can be applied to enlarge the production and so on. The mechanism of the alkenylation reaction is inferred from the literature and a series of controlled experiments, as shown in the figure below.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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