【作者】 刘平；

【导师】 王磊；

【作者基本信息】 淮北师范大学 ， 有机化学， 2011， 硕士

【摘要】 有机合成的核心任务是寻找有效的碳-碳键、碳-杂键生成方法和官能团相互间转换手段。相对于Pd和Ni来说,Cu是一种低毒并且廉价的过渡金属,如何使用Cu催化来实现碳-碳键、碳-杂键的偶联反应,不仅仅是过渡金属催化领域中的新趋势,也是化学工业绿色化进程中的一个挑战性课题。迄今为止,Cu催化的偶联反应已涉及碳-碳键、碳-氮键、碳-氧键、碳-卤键、碳-硫键、碳-硒键和碳-磷键的成键。三卤化铟作为温和的路易斯酸可在水、醇等绿色溶剂中实现高化学选择性、高区域选择性和高立体选择性的化学转化。三卤化铟在羟醛反应和类羟醛-曼尼希反应、付克反应、环氧化合物的重排反应、α-氨基膦酸的合成、喹啉环系的构建、酯交换反应、狄尔斯-阿德尔反应、手型呋喃二醇的合成、水相中的叠氮水解反应和二硫缩醛的制备中的应用,三卤化铟在有机合成中潜在的优势将推动“绿色化学”的发展。在本文中,主要研究以下内容:1.研究以硅胶负载的N-杂环卡宾铜配合物SiO₂-NHC-Cu（Ⅰ）为催化剂,苯硼酸和咪唑的偶联反应。此催化剂催化效率高,底物选择广谱性好,对芳基苯硼酸,脂肪苯硼酸,咪唑及其同系物都有良好的催化效果。该反应条件温和,反应操作简单,并且催化剂通过简单过滤回收,可循环6次使用而不失活,符合绿色化学的要求。2.研究以硅胶负载的N-杂环卡宾铜配合物SiO₂-NHC-Cu（Ⅱ）为催化剂,催化端基炔烃和亚磷酸酯的的偶联反应。此催化剂催化效率高,底物选择广谱性好,对芳基炔,脂肪炔都有良好的催化效果。该反应在空气中室温条件下进行,反应温和,操作简单,且催化剂可以循环6次使用不失活,符合绿色化学的要求。3.研究以三溴化铟催化的吲哚和α,β-不饱和酸酯的迈克尔加成反应,该反应具有反应条件温和,广泛的底物选择性,操作简单等优点。更多还原

【Abstract】 Transition metal-catalyzed coupling reactions represent an extremely versatile tool in organic synthesis. Due to their low price and toxicity, Cu salts have recently emerged as novel catalysts in coupling reactions of unsaturated carbons, whose replacement of toxic and expensive Pd and Ni catalysts will greatly improve the chemical industry in both the economic and environmental aspects. To date now, the development of the Cu catalysts in coupling reactions was summarized C–C, C–N, C–O, C–S, C–Se, C–P, as well as C–X coupling reactions. Indium tirhalide is a mild green catalyst for organic synthesis in a highly chemo-, region-, and stero-selectively fashion in green solvent such as aqueous and alcoholic media. In this paper, some applications of indium tirhalide in organic synthesis are rexiewed including aldol reaction, Friedel-Crafts reaction, the rearrangement of epoxides, the synthesis ofα-aminophosphonates, the synthesis of quinolines, the transesterification, the hetero Diels-Alder reaction, the synthesis of chiral furan diols, the azidolysis in aqueous media and the dithioacetalization. At the same time, our works on the application of indium trihalide in Biginelli reaction and reductive deoxygenation reaction area are also dicussed. The potential superiority of indium trihalide in organic synthesis will promote the development of“Green Chemistry”.In this thesis, The main works were summarized as follows:1. We have developed a new novel, practical and environmentally friendly method for the synthesis of N-arylazoles through a C-N coupling of azoles and arylboronic acids by using Silica–NHC–Cu(Ⅰ) as catalyst under air reaction conditions. The reactions generated the corresponding N-arylazoles in high yields and were applicable to Arylboronic acids. In addition, this methodology offers the competitiveness of recyclability of the catalyst without significant loss of catalytic activity, and the catalyst could be readily recovered and reused for six cycles, thus making this procedure environmentally more acceptable, whilst no catalyst leaching was observed.2. We have developed a new novel, practical and environmentally friendly method for the synthesis of alkynylphosphonates through a C-P coupling of terminal alkynes and H-phosphonates by using Silica–NHC–Cu(Ⅱ) as catalyst at room temperature under air reaction conditions. The reactions generated the corresponding alkynylphosphonates in high yields and were applicable to aromatic and aliphatic alkynes. In addition, this methodology offers the competitiveness of recyclability of the catalyst without significant loss of catalytic activity, and the catalyst could be readily recovered and reused for six cycles, thus making this procedure environmentally more acceptable, whilst no catalyst leaching was observed.3. A highly efficient synthetic strategy toward Michael addition of indoles toα,β-unsaturated esters has been developed using Lewis acid InBr3 as catalyst. The reactions generated 3-substituted indoles in high yields with excellent regio-selectivity in the presence of catalytic amount of InBr3 under mild reaction conditions. The method is simple, efficient and practical.更多还原