基于交叉脱氢偶联的串联环化反应研究

发布时间：2018-07-15 20:53

【摘要】：交叉脱氢偶联反应(CDC)直接通过两个C-H键结合,形成新的C-C键,避免了预先制备官能团化底物。因此,交叉脱氢偶联反应为有机合成提供了高效、环境友好的新途径。虽然交叉偶联反应从简单原料出发,通过C-H键直接官能团化,以很高的原子利用率合成了复杂化合物,但在该领域仍然要面临一些重大挑战。环状化合物是有机化合物中种类最多、数目最庞大的物种之一。许多天然产物和具有重要生物活性的药物及合成中间体都包含环状化合物骨架。如吲哚啉一1-酮骨架存在于很多天然产物中,具有异吲哚啉一1-酮亚结构的很多化合物显示出重要的药理活性。传统上,这些环状化合物主要是通过分子内成环反应或分子间多步反应来合成。这些方法在不同程度存在一些不足：包括原料不易得、反应条件苛刻、原子利用率低、三废排放量大。资源包括能源的有限性以及环境对污染忍受能力的有限性迫使人类发展高效、低耗、无排放的生产技术,绿色化学和可持续发展化学就是在这种背景下提出的新观念。因此,在环状化合物合成的研究和开发过程中,发展高效反应途径是实现环化反应绿色化的重要研究课题,对于绿色化学品的研究和开发、环境保护影响重大。基于此,本文主要研究了以下几个方面的工作：第一章主要介绍了过渡金属催化下交叉脱氢偶联反应的研究进展。第二章芳香羧酸、酰胺、二甲亚砜三组分通过Pummerer重排,实现了分子间的串联环化反应,合成了具有生物活性的异吲哚啉酮类化合物。该串联环化反应经历了分子间Csp~2-H/Csp~3-H的交叉偶联、C-N键的形成以及分子内的酰胺化反应。值得指出的是,在反应中二甲亚砜作为亚甲基给予体,反应无需加入催化剂和添加剂。第三章以简单易得的邻甲基苯甲酸为原料,[Cp*RhCl_2]_2为催化剂,碳酸银为氧化剂,二水合氯化铜为添加剂,利用芳香羧酸C(sp~2)-H键的氧化交叉脱氢偶联反应,成功的合成了4,8-二甲基联苯二甲酸酐,为联苯二甲酸酐类化合物的合成提供了一条简单方便的途径。第四章全文总结,对所做工作、结论以及创新点进行总结。
[Abstract]:The cross dehydrogenation coupling reaction (CDC) combines two C-H bonds directly to form a new C-C bond and avoids the preparation of the functional group substrate. Therefore, the cross dehydrogenation coupling reaction provides a new efficient and environmentally friendly way for organic synthesis. Complex compounds are synthesized by the utilization rate, but there are still some major challenges in this field. Cyclic compounds are one of the most species and the largest number of organic compounds. Many natural products and drugs with important biological activity and synthetic intermediates contain cytoskeleton. Such as indoline one 1- ketone skeleton. In many natural products, many compounds with isoindoline and one 1- ketone exhibit important pharmacological activity. Traditionally, these cyclic compounds are mainly synthesized by intramolecular ring reaction or intermolecular multistep reaction. These methods have some shortcomings in varying degrees, including raw materials and harsh reaction conditions. The limited nature of the atomic utilization rate and the high emission of three wastes. Resources including the limited energy and the limited environment for pollution tolerance compel human to develop high efficiency, low consumption, non emission production technology, green chemistry and sustainable development chemistry is a new concept under this background. Therefore, the research and development of cyclic compound synthesis In the process of development, the development of high efficiency reaction pathway is an important research topic for the realization of the green cyclization, which has great influence on the research and development of green chemicals and environmental protection. Based on this, this paper mainly studies the following aspects: the first chapter mainly introduces the research progress of cross dehydrogenation coupling reaction under the transition metal catalysis. In the second chapter, the three components of aromatic carboxylic acid, amides, and two methyl sulfoxide were rearranged through Pummerer rearrangement, and the intermolecular tandem cyclization reaction was realized. The biologically active isaindolone compounds were synthesized. The series cyclization reaction experienced intermolecular cross coupling of Csp~2-H/Csp~3-H, the formation of C-N bond and the amidation reaction in the molecule. In the reaction, two methyl sulfoxide was given as a methylene donor, and the reaction did not need to be added to the catalyst and additive. In the third chapter, the simple and easily available o methyl benzoic acid was used as the raw material, [Cp*RhCl_2]_2 as the catalyst, the silver carbonate as the oxidant, the two hydrated copper chloride as the additive, and the oxidation cross dehydrogenation coupling reaction of the aromatic carboxylic acid C (sp~2) -H bond, A successful synthesis of 4,8- two methyl biphenyl two methanic anhydride provides a simple and convenient way for the synthesis of biphenyl two formic anhydride. The fourth chapter is a summary of the work, the conclusion and the innovation point.
【学位授予单位】：陕西师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

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