可见光催化分子间的苯胺衍生物季烷基化

发布时间：2018-07-28 13:55

【摘要】：近年来,可见光催化作为一种新型绿色合成手段广泛应用到有机合成中。化石能源的枯竭与环境污染是当代社会面临的两大问题,而光能是一种廉价清洁的能源,取之不尽用之不竭,具有重要的应用前景。可见光催化化学反应与传统热化学反应不同,它是将光能转化为化学能,无需外加热源,同时反应条件更加温和,对许多官能团均具有较强的耐受性。全碳季碳中心结构广泛存在于天然产物分子和生物活性分子和药物分子中。构建分子间的全碳季碳中心一直是具有挑战意义的研究工作,也是有机合成化学的焦点之一。对于构建苯胺衍生物的苄基全碳季碳中心一直以来多是通过分子内的环化反应来实现的,如过渡金属催化的Heck反应、碳氢键活化、自由基串联反应等;近年来虽然可见光催化的有机合成方法学得到快速发展,但是光催化芳胺衍生物的季碳烷基化反应依然只发生在分子内的反应中。本论文主要研究了可见光催化芳胺衍生物分子间的季碳烷基化反应。N,N-二烷基苯胺衍生物与α-溴代酮在可见光催化条件下可以得到邻氨基芳环季碳烷基化产物,反应官能团耐受性好,产率优良。另外,该反应可以高产率实现克级规模及太阳光驱动反应。本文还通过光谱学方法、核磁滴定方法和Fukui指数计算方法对反应过程进行了探究。
[Abstract]:In recent years, visible light catalysis has been widely used in organic synthesis as a new green synthesis method. The depletion of fossil energy and environmental pollution are two major problems facing contemporary society. Light energy is a kind of cheap and clean energy, which is inexhaustible and has an important application prospect. The visible photocatalytic chemical reaction is different from the traditional thermal chemical reaction. It converts the light energy into the chemical energy without additional heat source, and the reaction conditions are more mild, so it has strong tolerance to many functional groups. The structure of whole carbon quaternary carbon centers is widely distributed in natural product molecules, bioactive molecules and drug molecules. The construction of intermolecular total carbon quaternary carbon centers has been a challenging research work and one of the focuses of organic synthesis chemistry. The construction of benzyl total carbon quaternary carbon centers of aniline derivatives has been achieved by intramolecular cyclization, such as transition metal catalyzed Heck reaction, hydrocarbon bond activation, free radical series reaction and so on. Although the method of organic synthesis catalyzed by visible light has been developed rapidly in recent years, the quaternary alkylation of aromatic amine derivatives only occurs in the intramolecular reaction. In this paper, the quaternary alkylation of aromatic amine derivatives with 伪 -bromoketone catalyzed by visible light was studied. The alkylation products of o-amino-aromatic ring quaternary carboxylation with 伪 -bromoketone were obtained. The reaction functional groups have good tolerance and yield. In addition, the reaction can achieve high-yield scale and solar-driven reaction. The reaction process was also investigated by spectroscopic method, nuclear magnetic titration method and Fukui exponent calculation method.
【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】：O621.251;O644.1

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