铑络合物催化磺酰亚胺导向的芳基碳—氢键官能团化反应研究

发布时间：2018-11-07 09:44

【摘要】：过渡金属催化的碳氢键活化是近年来有机化学中研究的最多、最热门的领域之一。通过过渡金属催化碳氢键官能团化的方法目前已经发展了很多,其中一种策略是通过导向官能团的特殊性质来实现。这种方法自日本化学家Murai在上世纪九十年代首创以来,一直被化学研究者所广泛使用。导向官能团的种类目前已经发展了很多种,主要的三大类就是氮、氧和硫原子。其中以氮原子作为导向官能团已经有了长足的发展,包括吡啶、吡咯以及嘧啶等。这些基团利用氮原子与过渡金属较强的配位能力来实现特定类型的碳氢键活化。但对于配位能力较弱的基团,如磺酰亚胺,其与过渡金属间较弱的配位能力导致这类基团的导向能力相对较低,所以目前通过使用这样一种氮类型的电子密度较低的基团作为导向来协助过渡金属催化的碳氢键活化的方法不多。本论文针对磺酰亚胺这样一类十分重要的化合物采用二氯(五甲基环戊二烯基)合铑(III)二聚体([Cp*RhCl2]2)作为催化剂来探索多种类型的碳氢键官能团化反应。这些研究包括了乙烯基化、烯丙基化以及利用交叉脱氢偶联反应来合成螺环类环状磺酰胺化合物。这些新的方法学不仅拓展了导向基团介导官能团化反应的多样性,而且也有利于对相关化学问题的深入理解。这些都将为后续更多新合成策略的探究奠定强有力的基础。在本论文的研究中,我们发展了一系列新的利用磺酰亚胺为导向基的过渡金属催化的方法学,包括烯丙基化、乙烯基化以及交叉脱氢偶联反应。在研究过程当中,我们系统考察了反应温度、时间、浓度、溶剂的种类、配料比、催化剂种类等因素对反应的影响,并利用NMR、LC MS以及HRMS等对产物的结构进行了鉴定。
[Abstract]:Carbon-hydrogen bond activation catalyzed by transition metals is one of the most popular fields in organic chemistry in recent years. Many methods have been developed to catalyze the functionalization of carbon and hydrogen bonds by transition metals. One of the strategies is through the special properties of the guided functional groups. This method has been widely used by chemical researchers since Japanese chemist Murai was first invented in the 1990 s. Many kinds of guided functional groups have been developed. The three main groups are nitrogen, oxygen and sulfur atoms. Among them, nitrogen atoms as the guiding functional groups have made great progress, including pyridine, pyrrole and pyrimidine. These groups make use of the strong coordination ability of nitrogen atoms with transition metals to realize the activation of specific types of carbon-hydrogen bonds. However, for groups with weaker coordination ability, such as sulfonimide, the weak coordination ability with transition metals results in a relatively low guiding ability of such groups. Therefore, there are few methods to assist transition metal-catalyzed carbon-hydrogen bond activation by using such a nitrogen-type group with low electron density as a guide. In this paper, dichloro (pentamethylcyclopentadienyl) rhodium (Cp*RhCl2) dimer ([Cp*RhCl2] 2) was used as catalyst to explore a variety of carbon-hydrogen bond functionalization reactions for a class of very important compounds such as sulfonimide. These studies include vinyl allylation and the synthesis of snails-like cyclic sulfonamide compounds by cross-dehydrogenation coupling reactions. These new methodologies not only expand the diversity of guided group mediated functional group reactions, but also contribute to the in-depth understanding of related chemical issues. All these will lay a strong foundation for further exploration of new synthesis strategies. In this paper, we have developed a series of new methods of transition metal catalysis based on sulfonimide, including allylation, vinyl and cross-dehydrogenation coupling reactions. In the course of the study, we systematically investigated the effects of reaction temperature, time, concentration, type of solvent, ratio of ingredients and type of catalyst on the reaction. NMR,LC MS and HRMS were used to identify the structure of the product.
【学位授予单位】：第三军医大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

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