【作者】 谢新刚；

【导师】 潘鑫复； 厍学功；

【作者基本信息】 兰州大学 ， 有机化学， 2006， 博士

【摘要】 本论文以MIRC反应在环丙烷合成中的应用和室温离子液中的Heck反应研究为主,共分为四章: 第一章 Domino反应研究进展及其在天然产物全合成中的应用(综述) 在这部分内容中,首先对Domino反应的定义,分类进行了介绍。然后依照分类标准,分别介绍了近年来正离子,负离子,周环,自由基,过渡金属催化,酶催化六类Domino反应在天然产物全合成中的应用。 第二章 利用MIRC反应高非对映选择性地合成1,2,3-三取代的环丙烷化合物 在这部分内容中,首先对MIRC反应进行了简介,并概述了MIRC反应在环丙烷合成中的应用。然后详细介绍了利用锂化的1,3-二噻烷与1,4-二芳基乙烯基环氧之间的MIRC反应高非对映选择性地合成1,2,3-三取代的环丙烷类化合物的研究工作。这个反应是一个Domino conjugation addition—epoxide opening的历程。该反应适用于1,4—双芳基乙烯基环氧化合物,具有很高的非对应选择性,在大多数例子中非对映选择性都在95:5左右。 第三章 室温离子液中的Heck反应研究 在这部分内容中,首先对绿色化学,室温离子液以及Heck反应做了简单介绍。然后详细叙述了以室温离子液为溶剂,对经典的C-C键构建反应(Heck反应)进行的研究工作,主要包括:(a)研究了微波促进下室温离子液中分子间的Heck反应,微波技术和室温离子液的应用,使得反应时间大为缩短;(b)研究了室温离子液中分子内的Heck反应,并将它应用在苯并呋喃类和吲哚类化合物的合成中,室温离子液的应用使得收率提高的同时,反应时间大为缩短,反应温度也有所降低。更多还原

【Abstract】 This Dissertation focuses on study of Formation of Cyclopropanes based on MIRC reaction and study of Heck reaction in room temperature ionic liquids. It contains four parts as follows:Chapter 1. The developments of Domino reaction and its applications in total synthesis of natural products (Review)In this part, the definition and classification of domino reaction were briefly introduced. Then cationic, anionic, pericyclic, radical, transition metal catalyzed, enzymatic domino reactions and their applications in the total synthesis of natural products were also reviewed.Chapter 2. A high diastereoselectively formation of 1,2,3-trisubstituted cyclopropane derivatives based on MIRC reactionIn this part, the MIRC reaction and its applications in synthesis of cyclopropanes were reviewed at first. Then our efforts of synthesis of 1,2,3-trisubstituted cyclopropane derivatives based on MIRC reaction between lithium 1,3-dithiums and 1,4-diary vinyl epoxides were discussed in details. This reaction was supposed to be a domino conjugation addition-epoxide opening sequence. This methodology can be applied to the 1,4-diaryl vinyl epoxides system. In most cases, the diastereoselectivity ratio was as high as 95:5.Chapter 3. Studies on Heck reaction in room temperature ionic liquidsIn this part, a brief introduction of green chemistry, room temperature ionic liquids and Heck reaction were presented at first. Then our efforts of applying ionic liquids as solvents in Heck reaction were discussed in details, which is the classic C-C bond formation reaction, (a) Pd/C catalyzed intermolecular Heck reaction in room temperature ionic liquids accelerated by microwave heating were developed. This methodology shortened the reaction time to 1.5 min with a modest yield, (b)Benzofiiran and indole derivatives were synthesized by Pd-catalyzed intramolecular Heck reaction in room temperature ionic liquids. The reaction time was shortened, the reaction temperature was lowered and the yields were improved by applying room temperature ionic liquids as solvents.Chapter 4, The total synthesis of nature occurring flavonolignan 5 " -methoxy-hydnocarpinIn this part, the benzodioxanelignans and the methods to synthesize them are reviewed at first. Then our synthetic effort towards the nature occurring flavonolignan 5 " -methoxy-hydnocarpin was discussed. The flavonolignan was obtained in 8 steps starting from 3,4-dihydroxy benzaldehyde, 2,4,6-trihydroxyl acetophenone and 3,4,5-trihydroxy benzaldehyde, in which the I2 oxidative cyclization and Ag2O oxidative coupling were the key steps. This synthetic route is convergent and can be applicable to synthesis of other benzodioxanelignans.更多还原