烯烃和肼衍生物应用于可见光催化的有机合成

发布时间：2018-04-24 15:18

本文选题：可见光催化合成吡唑 + 肼　；参考：《江苏大学》2017年硕士论文

【摘要】：可见光催化方法学是近年来发展起来的一种强大的合成手段,以其低能耗、无污染和原子经济性等特点而广受关注,给有机合成化学带来了新的机遇,已经在羰基的对映选择性α-官能化,[2+2]环加成,脱卤反应,芳香族化合物的自由基C-H官能化,脱羧偶联,以及在氧化偶联/环化协同催化中得到重要应用与发展。本论文利用可见光催化,通过对催化剂及反应条件的筛选,发展了吡唑类、酮类以及腙类化合物的高效绿色合成方法,主要工作包括以下几个部分:(1)可见光催化绿色合成吡唑类衍生物在论文第一部分中,我们发现了一种通过可见光催化肼与迈克尔受体生成吡唑类衍生物的高效绿色合成方法。该反应通过可见光催化将肼氧化为二氮烯,然后让其与迈克尔受体发生加成来形成吡唑,不同于传统的肼与羰基发生缩合反应。该合成方法反应条件非常温和,并且使用空气作为氧化剂,并具有原料易得、收率较高等优点,该方法开辟了吡唑合成的一个新领域。(2)可见光催化肼自由基加成合成酮类衍生物在论文第二部分中,我们发现了一种无金属参与,通过可见光催化氧化芳基肼形成自由基与烯烃发生自由基加成转化为酮类衍生物的新型合成方法。该反应操作简便性,普适性高,反应物价格低廉,副产物仅有氮气和水,绿色经济环保。反应能放大到20mmol,有着一定的潜在应用价值。(3)可见光催化氧化C=C键断裂合成腙类衍生物在论文第三部分中,我们发现了一种通过可见光氧化裂解碳碳双键构建腙类衍生物的方法。该方法使用空气中的氧气代替金属盐和有机过氧化物,用作烯烃和肼反应的终端氧化剂,反应条件温和,并且底物范围广泛,容易获得,普适性高,是一种新颖的高效温和合成腙类衍生物的方法。初步的机理研究表明了二氮杂环丁烷是该反应的中间体,这是一个重要突破,对于更进一步的研究有重要的借鉴意义。
[Abstract]:Visible-light catalysis is a powerful synthetic method developed in recent years. It has attracted much attention due to its low energy consumption, pollution-free and atomic economy, and has brought new opportunities to organic synthesis chemistry. It has been widely used and developed in enantioselective 伪 -functionalization of carbonyl group, [22] cycloaddition, dehalogenation reaction, free radical C-H functionalization of aromatic compounds, decarboxylation, and oxidative coupling / cyclization synergistic catalysis. In this paper, the efficient green synthesis methods of pyrazole, ketones and Hydrazone compounds were developed by using visible light catalysis and screening of catalysts and reaction conditions. The main work includes the following parts: 1) visible light catalyzed green synthesis of pyrazole derivatives. In the first part of this paper, we found a highly efficient green synthesis method of pyrazole derivatives by visible light catalysis of hydrazine and Michael receptor. In this reaction, hydrazine is oxidized to diazene by visible light and then added to Michael receptor to form pyrazole, which is different from the condensation reaction between hydrazine and carbonyl group. The reaction conditions of the method are very mild, air is used as oxidant, and the raw material is easy to obtain and the yield is high. This method opens up a new field of pyrazole synthesis. A new synthesis method for the oxidation of aryl hydrazine to ketone derivatives by visible light catalytic oxidation of aryl hydrazine and the addition of free radical to alkenes is described. The reaction is easy to operate, high universality, low price of reactants, only nitrogen and water by-products, green economy and environmental protection. The reaction can be amplified to 20 mmol, which has some potential application value.) in the third part of the thesis, we found a method to construct Hydrazone derivatives by visible light oxidation of C / C bond cleavage and synthesis of Hydrazone derivatives by visible light oxidation and pyrolysis of carbon and carbon double bonds. The method uses oxygen in the air instead of metal salts and organic peroxides as the terminal oxidant for the reaction of olefins and hydrazine. The reaction conditions are mild, and the substrate range is wide, easy to obtain, and the universality is high. It is a novel and efficient method for the synthesis of Hydrazone derivatives. The preliminary mechanism study shows that diazacyclobutane is the intermediate of the reaction, which is an important breakthrough, and has important reference significance for further study.
【学位授予单位】：江苏大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.37

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