本文選題：可見(jiàn)光氧化還原催化 + 光催化劑�。� 參考：《南京大學(xué)》2017年碩士論文

【摘要】：雜環(huán)化合物是一類重要的有機(jī)活性分子,廣泛存在于天然產(chǎn)物、藥物分子和具有生物活性的化合物中。因此,對(duì)于雜環(huán)化合物的合成已是有機(jī)化學(xué)界研究的熱點(diǎn)。在雜環(huán)合成的發(fā)展過(guò)程中,不同的催化體系及方法已經(jīng)被報(bào)道。近年來(lái),可見(jiàn)光敏催化已經(jīng)越來(lái)越受到合成化學(xué)界的關(guān)注,主要因其獨(dú)特的活化模式和綠色可持續(xù)的特點(diǎn)�？梢�(jiàn)光作為地球表面上的一種清潔、廉價(jià)且用之不竭的能源,近年來(lái)已經(jīng)成為化學(xué)家們研究的熱門話題。隨著人們對(duì)可見(jiàn)光促進(jìn)的氧化還原反應(yīng)的認(rèn)識(shí)不斷加深,可見(jiàn)光氧化還原催化在有機(jī)合成領(lǐng)域得到了迅速發(fā)展�？梢�(jiàn)光可以使反應(yīng)在溫和條件下進(jìn)行,但由于大部分有機(jī)物分子不能吸收可見(jiàn)光,限制了可見(jiàn)光的應(yīng)用,因此,光催化劑的提出將可見(jiàn)光催化在有機(jī)合成中的利用推向了高潮。光催化劑通過(guò)在可見(jiàn)光的照射下,變成激發(fā)態(tài),處于激發(fā)態(tài)的光催化劑可以與有機(jī)物分子發(fā)生單電子轉(zhuǎn)移或能量轉(zhuǎn)移從而實(shí)現(xiàn)整個(gè)催化循環(huán)過(guò)程。本論文主要介紹了可見(jiàn)光氧化還原催化的背景及機(jī)理,總結(jié)了雜環(huán)化合物的傳統(tǒng)合成方法,重點(diǎn)闡述我們研究的新的合成雜環(huán)的方法。本論文主要包含以下四部分內(nèi)容:第一章,總結(jié)可見(jiàn)光氧化還原催化的背景以及雜環(huán)化合物的應(yīng)用、研究進(jìn)展。第二章,可見(jiàn)光氧化還原催化的聯(lián)芳磺內(nèi)酰胺的合成,三嗪類化合物在激發(fā)態(tài)的光催化劑的作用下易脫去一分子氮?dú)猱a(chǎn)生自由基負(fù)離子活性中間體,該活性中間體可以高效地進(jìn)行分子內(nèi)的環(huán)合,最終以高收率得到目標(biāo)產(chǎn)物。第三章,可見(jiàn)光催化劑誘導(dǎo)下的2-溴-1,3-二羰基化合物與烯醇硅醚偶聯(lián)合成四取代呋喃,我們以2-溴-1,3-二羰基化合物為自由基前體,烯醇硅醚為電子受體,在可見(jiàn)光照射、光催化劑作用下以高收率得到多取代呋喃,底物適用性廣泛。第四章,可見(jiàn)光氧化還原催化的烯烴的氧化氨基化合成α-氨基酮,以苯乙�；Ｗo(hù)的羥胺衍生物為氮自由基前體,fac-Ir(ppy)3為光催化劑,DMSO為溶劑,又作為最終的氧化劑,在可見(jiàn)光的照射下完成烯烴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 偽 -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.
【學(xué)位授予單位】：南京大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O626

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