基于可见光氧化还原催化的杂环化合物的合成

发布时间：2018-04-21 16:17

本文选题：可见光氧化还原催化 + 光催化剂　；参考：《南京大学》2017年硕士论文

【摘要】：杂环化合物是一类重要的有机活性分子,广泛存在于天然产物、药物分子和具有生物活性的化合物中。因此,对于杂环化合物的合成已是有机化学界研究的热点。在杂环合成的发展过程中,不同的催化体系及方法已经被报道。近年来,可见光敏催化已经越来越受到合成化学界的关注,主要因其独特的活化模式和绿色可持续的特点。可见光作为地球表面上的一种清洁、廉价且用之不竭的能源,近年来已经成为化学家们研究的热门话题。随着人们对可见光促进的氧化还原反应的认识不断加深,可见光氧化还原催化在有机合成领域得到了迅速发展。可见光可以使反应在温和条件下进行,但由于大部分有机物分子不能吸收可见光,限制了可见光的应用,因此,光催化剂的提出将可见光催化在有机合成中的利用推向了高潮。光催化剂通过在可见光的照射下,变成激发态,处于激发态的光催化剂可以与有机物分子发生单电子转移或能量转移从而实现整个催化循环过程。本论文主要介绍了可见光氧化还原催化的背景及机理,总结了杂环化合物的传统合成方法,重点阐述我们研究的新的合成杂环的方法。本论文主要包含以下四部分内容:第一章,总结可见光氧化还原催化的背景以及杂环化合物的应用、研究进展。第二章,可见光氧化还原催化的联芳磺内酰胺的合成,三嗪类化合物在激发态的光催化剂的作用下易脱去一分子氮气产生自由基负离子活性中间体,该活性中间体可以高效地进行分子内的环合,最终以高收率得到目标产物。第三章,可见光催化剂诱导下的2-溴-1,3-二羰基化合物与烯醇硅醚偶联合成四取代呋喃,我们以2-溴-1,3-二羰基化合物为自由基前体,烯醇硅醚为电子受体,在可见光照射、光催化剂作用下以高收率得到多取代呋喃,底物适用性广泛。第四章,可见光氧化还原催化的烯烃的氧化氨基化合成α-氨基酮,以苯乙酰基保护的羟胺衍生物为氮自由基前体,fac-Ir(ppy)3为光催化剂,DMSO为溶剂,又作为最终的氧化剂,在可见光的照射下完成烯烃化合物的氧化氨基化。
[Abstract]:Heterocyclic compounds are a class of important organic active molecules, which widely exist in natural products, drug molecules and bioactive compounds. Therefore, the synthesis of heterocyclic compounds has been a hot topic in the field of organic chemistry. In the development of heterocyclic synthesis, different catalytic systems and methods have been reported. In recent years, it can be seen that Guang Min catalysis has attracted more and more attention in synthetic chemistry, mainly due to its unique activation mode and green sustainable characteristics. As a clean, cheap and inexhaustible energy source on the earth's surface, visible light has become a hot topic for chemists in recent years. With the increasing understanding of the visible light-induced redox reaction, the visible light redox catalysis has been developed rapidly in the field of organic synthesis. Visible light can make the reaction under mild conditions, but because most organic molecules can not absorb visible light, the application of visible light is limited. Therefore, the use of visible light catalysis in organic synthesis has been pushed to a climax. The photocatalyst can be transformed into excited state under visible light, and the photocatalyst in excited state can transfer single electron or energy with organic molecules to realize the whole catalytic cycle process. This paper mainly introduces the background and mechanism of visible light redox catalysis, summarizes the traditional synthesis methods of heterocyclic compounds, and focuses on the new synthesis methods of heterocyclic compounds. The main contents of this thesis are as follows: chapter one summarizes the background of visible light redox catalysis and the application of heterocyclic compounds. In the second chapter, the synthesis of biarylsulfonlactam catalyzed by visible light redox, triazines are easily removed from a molecule of nitrogen to produce free radical anion active intermediates under the action of excited photocatalyst. The active intermediate can efficiently carry out intramolecular cyclization and obtain the target product in high yield. In chapter 3, 2-bromo-1-oxo-3-dicarbonyl compounds coupled with enolosilyl ethers to synthesize tetra-substituted furans under visible light. We used 2-bromo-1-oxy-3-dicarbonyl compounds as free radical precursors and enolsilyl ethers as electron receptors, and irradiated in visible light. Under the action of photocatalyst, polysubstituted furan was obtained in high yield, and the substrate was widely used. In chapter 4, the oxidation of olefins catalyzed by visible light is used to synthesize 伪 -aminophenone, with phenylethane-protected hydroxylamine derivative as the precursor of nitrogen free radical and DMSO as the solvent and as the final oxidant. The oxidation of alkenes was accomplished by visible light irradiation.
【学位授予单位】：南京大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626

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