基于二氧化硫自由基历程构建磺酰官能团化反应的研究

发布时间：2019-02-12 23:03

【摘要】：二氧化硫广泛存在于大自然,作为S元素转化的重要形式,二氧化硫在远古时期人类先民在篝火活动时就已发现。然而二氧化硫同时也是大气污染的主要成分。现代工业的发展,导致了二氧化硫的大量排放,这些二氧化硫会在空气中转变成酸雨的主要成分硫酸。对树木、建筑、地表均造成巨大腐蚀。因此,二氧化硫治理是环境治理的重要部分。将二氧化硫应用到有机合成中正是其中途径之一。磺酰基是一类广泛存在于各类化合物中的结构,是常见的合成砌块,同时也是具有生物活性的结构。因此,研究磺酰基的构建方法一直以来都是个研究热点。二氧化硫插入其中一种很有效的方法。在过去的诸多研究中,己经有很多方法开发出来使用气体二氧化硫进行反应。由于气态二氧化硫的特殊性质,有毒不易控制,很不适合在实验室中使用,因此大大限制了其在有机合成领域的应用。近年来,二氧化硫载体试剂逐渐成为构建磺酰基的有效方法,相比以前的方法,插二氧化硫可以直接引入磺酰基而无需事先合成前体原料。大大拓展磺酰基的合成效率和底物适用范围。本文主要围绕固态二氧化硫载体作为磺酰源采用自由基串联的合成方法将磺酰基引入到有机小分子中。主要从以下两个方面展开工作:1、苯肼和偏亚硫酸钾在非金属参与的条件制备苯磺酰肼的反应研究开发了一种使用无过渡金属的氧化偶联反应,通过两种肼和焦亚硫酸钾在空气中合成的苯磺酰肼的方法。这种高选择性反应使用苯肼为芳基偶联的组分和焦亚硫酸钾作为二氧化硫的前体,它提供了一种新的安全绿色的合成策略来构建苯磺酰肼。2、基于DABSO通过铜催化的自由基氧化官能团化构建含磺酰官能团的不对称内脂的反应研究开发了一种基于二氧化硫载体DABSO通过与重氮盐、不饱和烯烃羧酸自由基串联环化过程构建含磺酰基的不对称内脂的方法。该方法首次实现将DABSO应用于不对称催化中。这种方法提供了一种在不对称内脂中直接引入磺酰官能团的方法。
[Abstract]:Sulfur dioxide exists widely in nature. As an important form of S element transformation, sulfur dioxide has been discovered in ancient times when the forefathers of man were active in bonfires. However, sulfur dioxide is also a major component of air pollution. The development of modern industry has led to massive emissions of sulfur dioxide, which can be converted into sulphuric acid, the main component of acid rain, in the air. The trees, buildings and the surface of the earth are corroded greatly. Therefore, sulfur dioxide governance is an important part of environmental governance. The application of sulfur dioxide to organic synthesis is one of the ways. Sulfonyl group is a kind of structure widely existing in all kinds of compounds. It is a common synthetic block and also has biological activity. Therefore, research on the construction of sulfonyl groups has always been a hot topic. Sulfur dioxide inserts one of these very effective methods. Many methods have been developed in the past to react with gaseous sulfur dioxide. Due to the special properties of gaseous sulfur dioxide, it is difficult to control the toxicity and is not suitable for use in the laboratory, so its application in the field of organic synthesis is greatly limited. In recent years, sulfur dioxide carrier reagent has gradually become an effective method for the construction of sulfonyl groups. Compared with previous methods, sulfur dioxide can directly introduce sulfonyl groups without the need to synthesize precursor materials in advance. The synthesis efficiency of sulfonyl groups and the application range of substrates are greatly expanded. In this paper, the solid sulfur dioxide carrier is used as a sulfonyl source to introduce the sulfonyl group into the organic small molecule by the method of free radical series synthesis. The main work is as follows: 1. The synthesis of phenylsulfonyl hydrazide from phenylhydrazine and potassium metasulfite under the condition of non-metallic participation. An oxidative coupling reaction without transition metal was developed. Benzenesulfonyl hydrazide was synthesized by two kinds of hydrazine and potassium pyrosulfite in air. This highly selective reaction, which uses phenylhydrazine as the aryl coupling component and potassium pyrosulfite as the precursor of sulfur dioxide, provides a new safe green synthesis strategy for the construction of phenylsulfonyl hydrazide. Based on the synthesis of unsymmetrical inner lipids containing sulfonyl functional groups by free radical oxidation of DABSO catalyzed by copper, a novel sulfur dioxide carrier, DABSO, was developed by using diazo salts. The method of constructing unsymmetrical internal lipids containing sulfonyl groups by series cyclization of unsaturated olefin carboxylic acid radicals. It is the first time that DABSO is applied to asymmetric catalysis. This method provides a method for directly introducing sulfonyl functional groups into asymmetric lipids.
【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】：O621.25

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