Hemicryptophane分子笼的合成及其在识别、分子机器和超分子催化的应用研究

发布时间：2018-03-09 04:04

  本文选题：Hemicryptophane　切入点：分子　出处：《华东师范大学》2017年博士论文　论文类型：学位论文

【摘要】：在主客体化学研究领域,hemicryptophane是一类结合了环三亚藜芦基和另一种C3对称结构单元的笼状化合物,近年来受到了人们广泛的关注。论文第一部分的第1章,概述了 hemicryptophane化学的研究进展,其中包括了该类笼状化合物的发展简史、合成方法、以及它们在分子识别、分子机器及超分子催化领域的应用。第一部分的第2章,提出了本论文的设想。本研究论文的目标是设计合成出新型的hemicrytophane化合物以达到更高效的分子识别和超分子催化性能。论文的第二部分主要研究了如何合理的设计、合成hemicryptophane化合物,以实现目标分子的选择性识别。第二部分共四章,编号分别为第3、4、5、6章。第3章设计合成了一个含萘荧光团和Zn(Ⅱ)金属配位中心的hemicryptophane笼状化合物,并研究了它作为荧光探针对磷酸胆碱两性离子在含水溶剂中的分子识别性能。因主体分子一端的环三亚藜芦基可结合铵根阳离子,而另一端的金属配位中心对阴离子具有结合作用,因此该主体化合物具有明显的两性分子识别特性。核磁和荧光光谱等分析测试表明该主体分子对磷酸胆碱两性分子具有选择性包结作用。第4章合成了两个以氟代苯环作为连接链的hemicryptophane主体化合物,并研究了它们对离子对客体的识别性能。该实验的设计目的是期望通过在苯环侧链上引入氟原子,提高其阴离子-π的结合力,进而提高主体分子一端对阴离子的结合能力。主体对阴离子结合性能的改变会导致其对离子对客体协同识别作用的调节,因此这些含氟主体对离子对的识别性能均与未含氟主体的识别性能进行了对比和结果分析。第5章合成了两个含三(2-吡啶基甲基)胺单元、具有两性识别特性的hemicryptophane笼状化合物。其中一主体以苯环作为环三亚藜芦基团和三(2-吡啶基甲基)胺单元的连接链;另一主体以萘环作为连接链,因此该主体具有荧光性能。由于环三亚藜芦基具有内在的螺旋手性,通过手性高效液相色谱仪成功的将合成的hemicryptophane外消旋混合物进行了手性拆分,分别获得了 hemicryptophane化合物的每个对映异构体。这些对映异构体在通过三(2-吡啶基甲基)胺单元络合金属离子之后,将会被进一步研究其对手性的两性离子的立体识别性能。第6章设计合成了 8个光学纯的hemicryptophane立体异构体。这些立体异构体含3种手性类型,分别为具有螺旋手性的环三亚藜芦基单元、具有轴手性的联萘基团和具有中心手性的三齿氨基三醇单元。通过化学交联的策略成功地归属了 8个立体异构体的绝对构型,并研究了该系列主体对糖类客体的立体选择性识别性能。第三部分唯一的一章,第7章,研究了一系列光学纯hemicrytophane化合物(第6章合成所得)分子的呼吸运动性能,弥补了 hemicryptophane在分子机器领域应用较少的现状。核磁和X-ray单晶衍射等分析手段表明这一系列化合物具有内凹的空间构型。而氧化钒与分子笼一端的三齿氨基三醇单元的配位使得内凹的分子笼充分的膨胀鼓起,分子笼内络合形成的氧化钒中心又可以被外来的三乙醇胺配体移除。因此通过外在因素,这些分子笼的空腔可以在内凹和鼓起两种稳定构型中循环往复多次,这种分子构型上的往复转换可被看作分子的呼吸运动。第四部分共三章,分别为第8、9、10章,研究了 hemicryptophane在超分子催化领域的应用。第8章报道了一系列氧化钒hemicryptophane络合物(第7章合成所得)在硫醚催化氧化反应中作为超分子催化剂的应用。结果表明,在钒催化活性中心上侧由联萘侧链和环三亚藜芦基单元所围成的疏水性空腔可极大提高硫醚氧化反应的产率、选择性和催化活性。第9章进一步将这些超分子钒催化剂应用于木质素模型化合物的催化氧化反应。与未含分子空腔的钒催化剂相比,超分子催化剂表现出明显的催化活性的提高,同时伴随着底物的非对映选择性转化的现象。第10章尝试性的研究了将氮磷川功能化的hemicryptophane化合物作为氢键供体有机催化剂用于交酯的开环聚合反应。结果表明,由于分子空腔的空间位阻,这类笼状催化剂表现出极低的催化活性。相反,未含分子空腔的氮磷川催化剂表现出令人满意的催化性能,同时我们提出了对应的催化反应机理。论文的第五部分仅一章,第11章,将研究的重点由hemicryptophane分子笼扩展到了自组装分子笼。通过多组分自组装策略,成功的将第10章介绍的氮磷川模块作为配体自组装成四面体金属胶囊;并且首次利用了氮磷川的氢键供体功能将氮磷川作为阴离子识别的受体;同时研究了氮磷川组装的四面体笼对阴离子的识别性能。除了介绍论文研究目的的第2章,其他所有章的研究内容均已发表或已整理好论文的形式准备发表。其中第1、3、4、5、6、7、8、10、11章已经正式发表,而第9章正在准备中。因此本论文的每章均保持了原发表文章的内容和书写逻辑,只对其进行了部分修改和补充。
[Abstract]:In host guest chemistry field, hemicryptophane is a kind of combined cage compound ring Sanya veratryl and another C3 symmetric structural unit, in recent years has aroused widespread concern. In the first chapter, the first part, summarizes the research progress of hemicryptophane chemistry, including the development history, the cage the synthesis methods and their applications in molecular recognition, molecular machines and supramolecular catalysis. The first part of the second chapter, put forward the idea of this thesis. This thesis aims to synthesize new compounds hemicrytophane to molecular recognition and supramolecular catalysis performance more efficient. The second part mainly studies how to design reasonable, the synthesis of hemicryptophane compounds, in order to achieve the selective recognition of target molecules. The second part consists of four chapters, numbered 3,4,5,6 Chapter. A naphthalene fluorophore and Zn synthesis of the third chapter design (II) hemicryptophane clathrate metal coordination center, and studied it as a fluorescent probe for molecular recognition properties of choline phosphate amphoteric ion in aqueous solvents. Because the main body at one end of the molecule around Sanya with resveratrol based ammonium cation, and the other end of the metal coordination center has combined effect on anion, so the host compounds have obvious characteristics of amphoteric molecular recognition. NMR and fluorescence spectrum analysis tests show that the host molecules with selective inclusion of phosphorylcholine amphiphilic molecules. The fourth chapter synthesized two with fluoro benzene compounds as the main body of the hemicryptophane connection the chain, and to study their recognition performance of ion on the object. The design purpose of this experiment is to hope that through the introduction of fluorine atom on the benzene ring in side chain, improve its anion - pi The binding force, and improve the binding ability of host molecules. End of the anion binding properties of the main changes to the anion can lead to the regulation of ionic synergetic recognition of the object, so these fluorine ions on the subject on the recognition performance and the recognition performance without fluoride are analyzed and the main results. Two the fifth chapter contains three synthesis (2- pyridyl methyl) amine units, hemicryptophane clathrates with gender recognition properties. One of the main in the benzene ring Sanya as resveratrol group and three (2- pyridyl methyl) amine chain connecting unit; the other main body with naphthalene as the connection chain, so the body has fluorescence properties. Because Sanya has inherent chirality veratryl, by chiral HPLC successfully hemicryptophane racemic mixture of chiral synthesis, were obtained from he Each compound micryptophane enantiomers. These enantiomers by three (2- pyridyl methyl) amine unit after complexation with metal ions, stereo recognition performance will be further studied on the chiral zwitterion. 8 optically pure hemicryptophane stereoisomers were synthesized. The sixth chapter designs these stereoisomers containing 3 kinds of chiral types, respectively with helical chiral ring Sanya veratryl unit with axial chiral binaphthyl chiral center group and having three teeth three amino alcohol units. Through chemical cross-linking strategy successfully belongs to absolute configuration 8 stereoisomers, and studied the performance of the stereo selective recognition the main object of sugar. Chapter third, only part of the seventh chapter, a series of optically pure hemicrytophane compounds were studied (Chapter Sixth obtained) respiratory motion performance of the molecule, make up for The current situation of hemicryptophane application in the field of molecular machines less. NMR and X-ray single crystal diffraction show that the spatial configuration of this series of compounds with concave and molecular. Three teeth amino vanadium oxide and molecular cage end of the three alcohol unit coordination makes concave cage heave sufficient, vanadium oxide molecular cage center the complex formation can be removed. Therefore foreign triethanolamine ligands through external factors, these molecules can include cage cavity concave and have two stable configurations in the cycle times, the molecular structure of the reciprocating change of respiratory motion can be seen as molecular. The fourth part consists of three chapters, respectively, chapter 8,9,10, research the application of hemicryptophane in the field of supramolecular catalysis. The eighth chapter reported a series of vanadium oxide hemicryptophane complex (the seventh chapter obtained) reaction in the catalytic oxidation of sulfide The application as supramolecular catalysts. The results showed that the catalytic activity of vanadium in upper center by binaphthyl side chain and ring Sanya veratryl unit formed by the hydrophobic cavity can greatly improve the sulfide oxidation reaction yield, selectivity and catalytic activity. The ninth chapter further oxidation of these supramolecular vanadium catalysts used in lignin model compounds. Compared with vanadium catalyst containing no molecular cavity, supramolecular catalysts exhibit catalytic activity obviously increased, accompanied by the substrate diastereoselective transformation phenomenon. The tenth chapter is the research on the hemicryptophane compounds of nitrogen and phosphorus Sichuan function as hydrogen bond donor organic catalyst for lactide. The ring polymerization reaction. The results show that the cavity due to the molecular steric hindrance, the cage catalyst showed low catalytic activity. On the contrary, not including the molecular cavity Nitrogen and phosphorus Sichuan catalyst showed satisfactory catalytic performance at the same time, we put forward the corresponding reaction mechanism. The fifth part is a chapter, the eleventh chapter, the focus of the study will be extended to the cage by hemicryptophane molecular self assembled molecular cage. Through multicomponent self-assembly strategies, the success of the tenth chapter n the Sichuan phosphorus module as ligand self-assembly into tetrahedral metal capsule; and the first use of nitrogen and phosphorus in the hydrogen bond donor function of nitrogen and phosphorus will Sichuan as anion recognition receptors; at the same time on the tetrahedral assembly of Sichuan cage nitrogen and phosphorus anion recognition properties. In addition to the introduction of the research purpose of the second chapter, all of the other chapters the research contents have been published or have collated the form for publication. The chapter 1,3,4,5,6,7,8,10,11 has been officially published, and the ninth chapter are prepared. Therefore this thesis of each chapter were maintained the original The content and writing logic of the article are published, and only part of it has been amended and supplemented.

【学位授予单位】：华东师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.3
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本文编号：1586886