过渡金属催化的碳氢键CO2羧基化固化反应研究

项目名称： 过渡金属催化的碳氢键CO2羧基化固化反应研究

项目编号： No.21472165

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 张玉红

作者单位： 浙江大学

项目金额： 85万元

中文摘要： CO2具有无毒、价廉、来源充足等优点，是理想的C1资源。但由于CO2特殊的动力学和热力学稳定性，使其活化固化面临诸多挑战。近年来，随着过渡金属催化理论和实验方法的飞速发展，人们在过渡金属催化的惰性碳金属键和碳卤键 CO2羧基化固化反应研究方面取得了突破性成果。这些转化底物广泛性好，选择性高、反应条件温和，已经成为固化利用CO2的有效途径。显然，通过C-H键直接进行CO2羧基化固化反应是更为直接经济的CO2固化利用方法。本项目拟采用各种不同过渡金属催化剂和典型C-H键活化反应底物，筛选各种含氮含磷配体，探索研究过渡金属催化的由C-H键直接与CO2反应进行CO2羧基化固化反应。深入研究其反应活性和选择性，总结其反应规律，揭示其可能的反应机理，发展和发现过渡金属催化的高效率、高选择性的C-H键CO2羧基化固化新反应，进而提供CO2固化新方法和新技术。

中文关键词： 有机合成方法学；过渡金属催化；绿色化学；C-H键活化；过渡金属

英文摘要： With the increasing awareness of the world's finite petroleum reserves, utilizing renewable resources is a prerequisite for a sustainable society of our world. Carbon dioxide (CO2) is an ideal C1 source owing to its abundance, low cost, nontoxicity, and good potential as a renewable source. However, it is not easy to activate such a thermodynamically and kinetically stable material. Numerous methods have been developed for CO2 fixation over the past decades. Among these methods, the transition-metal-catalyzed activation and conversion of CO2 into valuable chemicals that involve new carbon-carbon bond formation have recently emerged as extremely powerful tools because of their high chemoselectivity, good functional group tolerance, and mild reaction conditions. Obviously, the development of catalytic system for direct carboxylation via C-H bond activation will achieve the straightforward synthetic access for the fixation of carbon dioxide. In this project, we will study the carboxylation reaction of C-H bond by the use of transition metal (Cu, Pd, Ru, Rh, Ni, Fe and so on) as catalysts. We will investigate the reaction conditions and reaction mechanisms. We will examine the effect of catalysts and ligands, and obtain the optimal reaction conditions. Further more, we will establish the alternative approaches of fixation of carbon dioxide. The process of this project may lead to the creation of green and economical synthetic methods for fixation of carbon dioxide.

英文关键词： Organic Synthesis Methodology;Transition metal catalyzed;Green Chemistry;C-H Bond Activation;Transition metal