摘要
具有单一手性的光学活性的环芳(cyclophane)分子,诸如拓扑有趣的螺旋和笼状环芳分子是一类非常引人注目的分子母体,这不仅仅是因为其分子结构优美和在合成上富有挑战性,更重要的是它们独特的结构特征(如π共扼和螺旋手性等)预示出这类化合物作为新型功能材料的应用潜力。本论文在大量的文献调研和本实验室过去研究结果的基础上,设计了由2,2’-二取代-1,1’-联萘和2,6-二取代吡啶,1,4-二取代苯,4,4’-二取代联苯三种不同连接桥通过炔键链接构筑的拓扑有趣的光学活性环芳化合物-四联萘笼状分子。
在论文的第二章,主要讨论了具有单一手性[(R)构型或(S)构型]的2,2’-二乙炔基-1,1’-联萘模板的合成。从光学活性的2,2’-二羟基-1,1’-联萘出发,经过酯化,Kumada偶联,溴化,水解和Wittig消除反应五个步骤,成功地获得了具有单一手性的的2,2’-二乙炔基-1,1’-联萘。
在论文的第三章,为了实现目标分子的合成,设计了通过分子间氧化偶合成环反应得到目标分子的合成路线。由于拓扑的要求是目标化合物必须是相互缠绕而形成的环状分子,这就需要获得一些重要的中间体,而这些中间体通常需要控制合成。该路线经过保护基(TMS)的导入,连接桥的导入,保护基的脱除以及铜盐催化的炔烃分子间偶合成环反应,最终获得了如下所示的几个四联萘笼状目标分子。所有的目标化合物的结构经过~1H NMR,~(13)C NMR和DEPT组合测定以及IR得到确认。并通过计算化学的方法对目标分子结构进行了模拟。
Optically active cyclophanes, such as helical molecules and three-dimensional, cagelike cyclophanes have been the subject of extensive investigation from the standpoints of structural chemistry and material science. The fundamental sources of the interest in cyclophanes include the conception of novel, aesthetically pleasing and interesting structures, the challenge of synthesizing them, and the study of their properties once they had been prepared. Their unique structural features (π-conjugated, helicity) indicate their potential applications in optics and electronics. In this thesis, based on the preceding research of our laboratory, a new type of cagelike cyclophanes, in which 1,1 '-binaphthyl unit ,the source of chirality and three different linkers(2,6-dibromopyridine, 1,4-diiodobenzene, 4,4'-diiodobiphenyl) connected by ethynyl was designed and synthesized successfully and their optical properties were preliminarily researched.In the second chapter, a rational synthetic route for enantiopure 2,2'-diethynyl-1,1 '-binaphthyl was established. From the optically active 2, 2'-dihydroxy-1,1 '-binaphthyl, through esterification, Kumada coupling, bromization, hydrolization and Wittig elimination reaction, 2,2'-diethynyl-1,1'-binaphthyl was obtained.In the third chapter, in order to synthesize the target molecules, a intermolecular oxidative coupling route was designed . Some important intermediates should be obtained to fit the topological demand of the target molecules. The synthetic route includes four general reactions. Monosilylethynyl derivative was obtained first, then exposure of this compound to three different linkers separately under Sonogashira reaction condiction, after removal of protective group under mild condition, the diacetylene intermediates were obtained successfully. The diacetylenes were then added to a solution of Cu(0Ac)2 in pyridine by syringe pump to achieve pseudo high dilution conditions to minimize polymerization of the starting material. Then three kinds of cagelike target molecules were obtained finally. The structures of the new intermediates and target molecules were identified by IR, ~1H NMR, ~(13)C NMR, ~(13)C DEPT NMR and the structures of target molecules were simulated in a computational chemistry way.
引文
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