【作者】 刘建立；

【导师】 曾润生；

【作者基本信息】 苏州大学 ， 有机化学， 2010， 硕士

【摘要】 C-S键、C-C键、C-N键广泛存在于许多有生理活性的天然产物、药物、农药以及具有电子性能的材料中,因此C-S键、C-C键、C-N键构建方法,对合成含有这些结构单元的天然产物、药物、农药、材料等非常重要,从而一直是有机化学家重点研究的课题之一。Ullmann反应是形成C-S键、C-C键、C-N键的重要方法。但是传统Ullmann反应须高温,强碱,以及催化剂过量的条件下反应,且产物收率不高。为了克服这些缺点,我们在本课题组的实验基础上探索了新的温和的,适用范围比较广的C-S、C-C、C-N的成键方法。1.卤代芳烃与硫酚,硫醇的偶联反应。以二价铜离子为金属离子,2,2’-联咪唑为配体,卤代芳烃和硫酚,硫醇为原料,合成了一系列芳基硫醚化合物。该体系比较新颖,反应条件温和,反应时间短,催化效果好。2.卤代芳烃与与活性亚甲基化合物偶联反应。在二价铜离子和1,1’-三亚甲基-2,2’-联咪唑催化下,卤代芳烃与乙酰丙酮进行反应,以较高的产率得到了一系列3-芳基-2,4-戊二酮类化合物,该反应未见有二价铜离子报道。3.卤代芳烃与含氮杂环的偶联反应。以Cu(acac)2和金属Ni为催化剂,卤代芳烃与含氮杂环为原料,高效的得到了一系列N-芳基杂环化合物。与其它过渡金属催化的N-芳基化反应相比,该体系比较新颖,廉价易得,反应条件温和,不需要惰性气体保护,对底物的适用范围比较广泛。更多还原

【Abstract】 C-S, C-C and C-N bond have always been a vital part in many natural pharmaceticals, drug and electronical materials, and thus the synthesis method of C-S, C-C and C-N is critical due to its widely application in constructing a series of structural units in natural product, pharmaceticals, drugs for plants and material chemistry. Ullmann type reaction is an important way to form C-S, C-C, and C-N bond. Despite an inferior yield, this method requires a high temperature, an existance of alkali and an excess of catalysts. To overcome those disadvantages, our group explored a novel way as follows which can be conducted in mild condition with a more wide application of substrate generality.In the first chapter, a series of thiother derivatives have been synthesized by the coupling of aryl halides wih aryl or alkyl thiols under the assistance of Cu(OAc)2·H2O /2,2’-biimidazole. The catalysitic system shares a reputation for novelty, lower cost, lower reaction temperature and shorter reaction time.In the second chapter, a mild, simple and efficient way was developed to carry outα-aryl carbonyl compounds synthesis, which is applicable to a large variety of substrates with different functional groups. This simple active catalytic system represents the first report of C-C bond formation using Cu(OAc)2·H2O.In the third chapter, a series of N-aromatic heterocycle compounds have been synthesized by the reaction of aryl halides and nitrogen heterocycles by using Cu(acac)2/Ni. The method is proved to be novel with a comparable cost advantage in mild condition, and it also can be conducted without the protection of inert gas and applied to a wide substrates generality.更多还原