【作者】 于华；

【导师】 谢如刚；

【作者基本信息】 四川大学 ， 有机化学， 2006， 博士

【摘要】 环糊精及其衍生物在酶模拟，催化，药物输送等方面有着多种的用途。环糊精经化学修饰后可以衍生出各种各样的分子，不仅可以改变其分子的构型，而且可以改变分子尺寸，改善环糊精对客体分子的选择性。但是由于环糊精有众多的羟基，因此对环糊精进行选择性的修饰仍然是一个难点。本文探索了选择性修饰环糊精的方法；合成了丹酰修饰的环糊精衍生物，研究了其在化学发光中的应用，取得了一系列具有重要学术意义的创新性结果。主要内容包括以下几个部分：1．简要介绍了选择性修饰环糊精以及化学修饰环糊精在超分子化学方面的应用。2．探索了一种简便合成2位环糊精单磺酸酯和全磺酸酯的方法。使用碳酸铯作为催化剂，在DMF中可以有效的催化β-环糊精和磺酰化咪唑的反应，生成环糊精2位的磺酸酯。这一方法具有反应快速、产物不复杂、操作方便和结果稳定的特点。应用此方法，我们首次实现了在无保护条件下环糊精2位羟基的全部磺酰化，并且可以得到较好的收率。3．合成了由构型控制的第一面修饰的γ-环糊精内酯。在γ-环糊精的一个糖单元(A环)的6位引入半胱氨酸的丹酰胺这个化合物在和环糊精的邻近两个糖单元(B环和G环)上的6位羟基反应生成内酯的过程中，表现出了顺一反时针的选择性，只和B环上的羟基发生反应。大体积的丹酰基团在这个反应中可能起到了重要作用。4．合成了四类13个新型丹酰修饰的环糊精，其中包括在β和γ-环糊精的不同面上取代的单功能化环糊精、含有咪唑基和丹酰的双取代β-环糊精、盖帽的β-环糊精，以及桥连的γ-环糊精。并且借助核磁，质谱等分析手段，对化合物的结构进行了表征。5．研究了丹酰修饰环糊精在化学发光中的应用。结果表明，β-环糊精3位的丹酰胺可以与反应物生成化学计量比为1∶1的配和物。考察了环糊精对化学发光反应的两个阶段：荧光和化学激发的影响。β-环糊精3位的丹酰胺比参比化合物Dansyl glycine的化学激发效率提高了2倍。利用圆二色谱推断了所选的环糊精衍生物的构型，对实验的结果做了进一步的说明。更多还原

【Abstract】 Cyclodextrins and their chemically modified derivatives are widely used in artificial enzymes, catalyze, drug carrier, etc. Cyclodextrins can be subjected to diverse modifications to give a wide variety of cyclodextrin derivatives, which could alter the conformation, size and the molecular selectivity of the guest molecular. Selective modified cyclodextrins is also difficult own to the numerous hydroxyl of it. In this thesis a facile method of synthesing mono- and per（2-sulfonyl）-β- cyclodextrins was afforded, and a series of dansyl modified cyclodextrins were synthesed which were subjected to the chmiluminesence reaction. A series of useful and creative results have been obtained. The major contents are as follows:1. The general aspect of the mothed of selective modifying cyclodextrin and their use in supramolecular chemistry.2. Afford a facile syntheses of mono- and per（2-sulfonyl）-β-cyclodextrinso Cs₂CO₃ was found to efficiently catalyze the reaction ofβ-cyclodextrin and N-tosylimidazole. This methodology has the advantage of a fast and clean reaction, facile manipulation and stable results for the monosulfonates.lt also ensured the first direct sulfonylation of all the 2-OHs.3. Efficient topological control in the syntheses of cappedγ-cyclodextrins. Modified one glucose unit（A） ofγ-cyclodextrin with N-dansyl-L-cysteine, in the precess of esteri-fition the flexible cysteine moiety can differentiate hydroxyl groups in clockwise -counterclockwise relationship led to the reaction of only 6^B-OH among many others, affording the corresponding lactone. The bulky dansyl group is supposed to display an important role in control the regio-selectivity.4. Four kinds, thirteen novel cyclodextrin derivatives, including mono-modifiedβ-cyclodextrin and -cyclodextrin on the different rims, imidazole and dansyl dimodifiedβ-cyclodextrin, capped cyclodextrin and bridgedγ-cyclodextrin, and their structures were characterized by NMR, MS.5. Chmiluminesence properties of the dansyl modified cyclodextrins were examined, the results show that 1:1 in inclusion complexes are formed for the 3-dansyl-β-cyclodextrin with TCPO. The influence of cyclodextrin on the fluorescence and the chemiexcitation were also examined. Campared with dansyl glycine, compound 3-dansyl-β-cyclodextrin showed 2 times enhancement of chemiexcitation. The conformation of cyclodextrin derivatives were elucidated by spectropolarimetric, and further explaination were also gived.更多还原