铜催化构建C-S和C-N键的反应研究（Study on the reaction of C-S and C-N bonds catalyzed by copper）.pdfVIP

摘 要 过渡金属催化的交叉偶联反应是构建碳-碳键、碳-杂键最为有效的手段之 一，已经被广泛地应用于有机化学的许多领域。近几十年来，人们主要集中于用 各类配体的合成来提高过渡金属的催化活性和底物的适应性，而对开发更简便、 且环境友好的新型催化体系的研究相对薄弱。 同时，与钯、镍等过渡金属相比, 铜是一种廉价且毒性低的金属, 而且可以减少对环境的污染, 促进绿色化学的 发展。基于这两点，本论文主要研究了在不同反应体系中，铜催化碳-硫键和碳- 氮键的构建，主要研究内容如下： 首先，我们研究了以 PEG-400/H O 为反应介质，铜催化芳基卤与硫代乙酸 2 偶联反应合成芳基硫醚的反应。我们考查了不同取代基的芳基碘、芳基溴与硫代 乙酸的反应，研究发现：该催化体系具有广泛的官能团容忍性，可获得高达 96% 收率。 其次，我们研究了以 PEG-400 为反应介质，无配体、铜催化芳基卤与水合 肼偶联反应合成芳基肼的反应。我们考查了一系列芳基卤的电子效应、空间效应 对催化活性的影响，均获得了令人满意的实验结果，可获得高达 91%的收率。同 时，对该反应的机理进行了探索。 最后，我们研究了铜催化腙类化合物与 2-巯基苯并噻唑的高选择性构建 C-S 键。我们发现相应的醛、酮腙都能与 2-巯基苯并噻唑发生偶联反应。 关键词：铜催化；交叉偶联；PEG-400 ；选择性 I Abstract The transition-metal-catalyzed cross-coupling reactions are simple, efficient, and versatile routes to the formation of carbon-carbon and carbon-hetero bonds, which represents the key step in a wide range of preparative organic processes. In last decades, many chemists mainly focused on design and synthesis of different kinds of ligands. However, study of more convenient and environment-friendly catalytic system is relatively rare. In comparison with Pd and Ni, copper is a cheap metal with low-toxicity. In this thesis, we have investigated the copper-catalyzed C-S and C-N bonds coupling reactions in novel reaction systems. The details are summarized as follows: First, a simple and highly efficient catalytic system for synthesis of diaryl Sulfides by copper-catalyzed coupling of aryl halides and thioacetate in PEG-400/ H2O media was developed. A variety of aryl halides could be reacted with thioacetate to give the desired products in high yields up to 96%. The present catalysis protocol tolerated a wide scope of functional grou