碘苯对位C-H键以及烯烃C=C键选择性氧化官能团化反应的研究

发布时间：2018-04-21 05:25

本文选题：碘苯 + 对位碳氢键　；参考：《江西师范大学》2017年硕士论文

【摘要】：众所周知有机合成是有机化学中的精髓,那么反应选择性的调控毫无疑问是有机合成领域中最重要的挑战。高选择性有机合成使得合成化学更加绿色、高效,具有原子经济性。目前化学反应选择性的研究和应用均取得了很大的进展,并且展现出了不少调控规律,但是目前反应选择性的研究仍然存在许多问题和缺陷,例如需要使用昂贵有毒的催化剂,底物适用范围有限,反应条件较为苛刻,选择性控制仍然较差等,同时人们对许多反应选择性的现象仍然了解不够,尚未进行深入研究和解释。基于现状,本论文尝试发展新的简便温和高效的控制选择性的方法,以促进有机合成选择性的研究。本论文首先综述了芳烃化合物C-H键选择性官能团化和烯烃C=C键选择性官能团化两大类选择性合成反应。通过总结以上选择性合成反应的规律,设计合理的选择性合成方法,积极的实验探索和机理研究,本论文找到了两类新的简便高效的选择性合成方法,分别是碘苯对位C-H键选择性官能团化以及烯烃C=C键选择性氧化官能团化制备三取代乙醛。论文研究主要获得以下结果:1.设计了一种两电子转移的氧化还原方式来实现碘苯的对位选择性C-H键活化。该反应条件温和,不需要任何金属催化剂,正丁酸可以对反应产生很好的促进作用。自由基抑制实验表明该反应过程中很可能不涉及自由基过程,在线红外和核磁研究表明正丁酸和亚碘酰苯反应形成的中间体是这个反应的关键。2.利用廉价易得的铁催化剂催化烯烃C=C键选择性氧化官能团化合成2,2-二芳基-2-(四氢呋喃-2-基)乙醛。该方法不仅实现了强氧化体系中醛的合成,而且一步实现了两个季碳中心的构建,具有非常重要的合成意义。
[Abstract]:As we all know that organic synthesis is the essence of organic chemistry, the regulation of reaction selectivity is undoubtedly the most important challenge in the field of organic synthesis. High selective organic synthesis makes synthetic chemistry more green, efficient, and atomic economy. The research and application of chemical reaction selectivity has made great progress, and There are many regularities of regulation, but there are still many problems and defects in the study of reaction selectivity, such as the need to use expensive and toxic catalysts, the limited scope of the substrate, the harsh reaction conditions, the poor selective control and so on. At the same time, people still don't know enough about the selectivity of many reactions. Based on the present situation, this paper attempts to develop a new, simple and efficient method of controlling selectivity in order to promote the selective study of organic synthesis. In this paper, the two major selective synthesis reactions of aromatic compounds C-H bond selective functionalization and olefin C=C bond selective functionalization are summarized. Above the rules of selective synthesis, a reasonable selective synthesis method, a positive experimental exploration and a mechanism study, two new and simple and efficient selective synthesis methods are found in this paper, which are the selective functionalization of the C-H bond of iodine, and the preparation of three substituted acetaldehyde by the selective oxidation of olefin C=C bond. The main results are as follows: 1. a redox method of two electron transfer was designed to realize the activation of the counterpart selective C-H bond of iiphbenzene. The reaction condition is mild, no metal catalyst is needed, and n-butyric acid can promote the reaction very well. The free radical inhibition experiment shows that the reaction process may not be involved in the reaction process. The free radical process, on line infrared and nuclear magnetic studies show that the intermediate of butyric acid and iodide benzene reaction is the key.2. of this reaction, which catalyzes the selective oxidation of olefin C=C bond to synthesize 2,2- two aryl -2- (tetrahydrofuran -2- based) acetaldehyde by the cheap and easy iron catalyst. This method not only realizes the aldehyde in the strong oxidation system. The synthesis of the two quaternary carbon centers is also of great significance.

【学位授予单位】：江西师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25

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