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1、硕 士 学 位 论 文论文题目: 水解酶的催化多功能性及其串联方法的研究作者姓名 指导教师 学科(专业) 应 用 化 学 所在学院 理 学 院 提交日期 2011 年 1 月 M. S. DissertationStudy on the Catalytic Promiscuity of Hydrolase and Tandem Reaction Author: Xiang ChenAdvisor: Prof. Xianfu Lin Chemistry Department, Zhejiang UniversityJan 2011Hangzhou China独特性声明附件3：独创性声明与版权使用
2、授权书独创性声明本人声明所呈交的学位论文是本人在导师指导下进行的研究工作及取得的研究成果。据我所知，除了文中特别加以标注和致谢的地方外，论文中不包含其他人已经发表或撰写过的研究成果，也不包含为获得 浙江大学 或其他教育机构的学位或证书而使用过的材料。与我一同工作的同志对本研究所做的任何贡献均已在论文中作了明确的说明并表示谢意。 学位论文作者签名： 签字日期： 学位论文版权使用授权书 本学位论文作者完全了解 浙江大学 有关保留、使用学位论文的规定，有权保留并向国家有关部门或机构送交论文的复印件和磁盘，允许论文被查阅和借阅。本人授权 浙江大学 可以将学位论文的全部或部分内容编入有关数据库进行检索，
3、可以采用影印、缩印或扫描等复制手段保存、汇编学位论文。 （保密的学位论文在解密后适用本授权书） 学位论文作者签名： 导师签名： 签字日期： 签字日期： 学位论文作者毕业后去向： 工作单位： 电话： 通讯地址： 邮编：i摘要摘要酶催化有机合成方法的研究越来越受化学家关注，探索酶催化的新功能，调控酶促反应，通过酶催化多功能性来设计串联反应新方法新途径；为化学的绿色合成提供更有价值的新思路、新技术。论文研究了脂肪酶催化Friedel-Crafts烷基化反应的新功能，考察了反应条件，包括反应时间、酶源、溶剂、底物的比例、酶浓度、温度、底物结构对脂肪酶催化Friedel-Crafts烷基化反应的影响，合
4、成了15种吲哚衍生物。并通过无酶，BSA及失活的PPL来验证酶活性中心的催化作用，提出了可能的催化机理。论文研究了脂肪酶催化的亲核加成-消去-Michael加成串联反应的新功能，考察了酶源、反应介质、混合溶剂的比例、酶浓度、温度、反应时间、底物结构对脂肪酶催化该串联反应的影响，结果表明：在水与二氧六环比例为4/1的混合溶剂中，脂肪酶PPL可以催化醛与吲哚的串联反应，合成了26种双分子吲哚衍生物。论文研究了N-杂环化合物添加对酶促反应的调控作用。发现当酶与咪唑质量比为2/1时，酰化酶的催化Claisen-Schmidt活性显著提高。并通过无酶无咪唑、BSA和咪唑、单酶及单咪唑催化来证实酶活性中心
5、和咪唑的共同的催化作用，提出了可能的催化机理。同时考察了酶源、溶剂、添加剂、反应时间、底物结构对酰化酶与咪唑催化反应的影响；并合成了18种, -不饱和羰基化合物。论文通过调控酰化酶与咪唑共同催化催化芳香醛与酮的Aldol缩合-消去-Michael加成-分子内Aldol缩合-消去串联反应活性，合成了15种新颖的环己烯酮衍生物。考察了反应条件：酶源、溶剂、添加剂、酶与添加剂的比例、底物结构对酰化酶与咪唑催化串联Aldol缩合-消去-Michael加成-分子内Aldol缩合-消去反应的影响，并提出了可能的反应机理。本论文总共合成了74种化合物，产物经IR，1H-NMR, 13C-NMR，GC-MS，
6、HRMS等手段表征分析和验证。关键词：脂肪酶、酰化酶、串联反应、多功能性、共同催化。101浙江大学硕士学位论文AbstractEnzyme catalysis in organic synthesis had drawn an increasing number of chemists attention. Explore new function of enzymes; regulate enzymatic reaction; design a new tandem reaction base on the promiscuity of enzym, providing more valua
7、ble, new ideas and new technologies for green chemistry.Lipase was firstly found to catalyze the Friedel-Craft reaction in water. After screening the reaction time, enzyme sources, reaction media, the molar ratio of substrate, temperature and the structure of substrates, lipase from porcine pancreas
8、, Type II (PPL) catalyzed the Friedel-Craft reaction of indole derivative and , -unsaturated compounds. 15 Fridel-Craft adducts were synthesized. The control experiments proved that the active site of PPL were responsible for those enzymatic reaction. The mechanisms for the Friedel-Craft reaction an
9、d tandem reaction catalyzed by PPL were also proposed.We screening the PPL catalyze the tandem Nucleophilic addition/dehydration /Michael addition of aldehyde and indole. The enzyme sources, reaction media, temperature, the structure of substrate that affects this tandem reaction were investigated s
10、ystemly. In mixture solvent (water/dioxane=4/1), lipase (from porcine pancreas, Type II) can catalyze the tandem Nucleophilic addition/dehydration /Michael addition between aldehydes and indole derivatives. After the stepwise process were optimized, 26 bis(indolyl)alkanes were prepared in moderate t
11、o excellent yields by using PPL as catalyst.The influence of N-heterocyclic compounds on the enzymatic reaction was investigated. Though investigating enzyme sources, solvent, additive, the ratio of imidazole and acylase, we found D-aminoacylase and imidazole can co-catalyze the Claisen-Schmidt reac
12、tion. When the ratio of D-aminoacylase and imidazole is 2/1, the activity of D-aminoacylase was improved obviously. And 18 tandems Aldol condensation/dehydration adducts were obtained via this method. The control experiments demonstrated that the active site of D-aminoacylase was responsible for the
13、 enzymatic reaction. The mechanism for the Claisen-Schmidt reaction catalyzed by D-aminoacylase and imidazole was also proposed.A single enzyme can co-catalyze the cascade Aldol condensation-elimination -Michael-intromolecular Aldol condensation-elimination for synthesis of conjugate cyclohexanone-2
14、-ene reaction with imidazole in octane. By investigating enzyme sources, solvent, additive, the ratio of imidazole and acylase, we found D-aminoacylase and imidazole can co-catalyze this tandem reaction. After the stepwise process was optimized, 15 conjugate cyclohexanone-2-enes were prepared. Some
15、control experiments were designed to prove that the enzyme can co-catalyze this cascade reaction with imidazole in octane. The mechanism for the tandem reaction catalyzed by D-aminoacylase and imidazole was also proposed.In this thesis, 74 compounds were synthesized and these compounds were characterized by IR, 1H NMR, 13C NMR, GC-MS and HRMS.Keywords: lipase; acylase; tandem; multifunctio
