金属催化的烯烃上碳氟键的还原及烷(芳)基化

The activation of inert chemical bonds is an area of current interest, especially the activation of carbon-fluorine bonds, which is a challenging research field. Despite such encouraging developments of C-F bond activation in aromatic fluorides, examples of C-F bond activation in fluoroalkenes remain very scarce. In this project, we focused on the activation of carbon-fluorine bond in fluoroalkenes based on previous studies. According to the properties of C-F bonds in fluoroalkenes, which is different from C-F bonds in aromatic fluorides, we try to develop novel reaction systems for C-F bond hydrodefluorination and functionalization in fluoroalkenes: 1. We try to use the common metal catalysts such as iron, nickel and cobalt salts etal. and simple reductants to carry out the hydrodefluorination of C-F bond in fluoroalkenes in more mild and cheaper way. 2. We try to design efficient and convenient catalytic reaction systems for Kumada and Negishi reaction of C-F bonds in fluoroalkenes by using commom and cheaper metal catalyst. Meanwhile, the key issue of the activation and essentials of C-F bond will be further investigated through the probe of the reaction mechanism. We are aimed to develop novel reaction system for the activation of C-F bond in different kinds of fluorides, and accumulate experience of C-F bond activation by the implement of this project.

惰性化学键的活化是当前有机合成的前沿研究领域，而碳氟键的活化是其中极具挑战意义的研究内容。目前，有关碳氟键活化的研究主要集中在含氟芳烃的碳氟键上，而对烯烃上碳氟键的活化研究相对较少。本项目在申请人前期含氟芳烃的碳氟键活化的工作基础上，拟开展针对烯烃上碳氟键的碳氢化和官能团化的研究。根据烯烃上碳氟键在化学反应能力和稳定性不同于芳烃上碳氟键的特点，设计筛选出1.更温和、价廉的催化还原烯烃上碳氟键为碳氢键的反应体系，其中催化剂拟优先选用普通的金属催化剂(如铁、镍、钴等)，避免使用昂贵的金属盐络合物、复杂的配体；并尽量使用简单、操作方便、有实用前景的还原剂。2.高效、简便的将烯烃上碳氟键进行Kumada和Negishi交叉偶联反应的不同催化体系。另外，本项目还拟对相应的反应的催化机理做初步的探讨。通过本项目的实施，可以进一步拓展碳氟键活化的研究范围，并为更深入理解碳氟键的本质及其活化条件积累经验。

惰性碳氟键的活化是有机氟化学的热门研究领域之一，sp2杂化的烯烃碳氟键的活化研究相对于其他碳氟键的活化研究较少。本项目致力于系统地开展sp2杂化的烯烃碳氟键的活化体系研究，发展出了用红铝选择性地还原二氟烯烃上单个C-F键的温和的反应体系以及钯和镍金属催化烯烃碳氟键的活化并进行官能团化的反应体系，具体为筛选出了钯金属催化的含氟烯烃与不含β-H的格氏试剂以及镍催化的二氟烯烃与含β-H的格氏试剂进行Kumada偶联的两个反应体系，并开发了镍金属催化的二氟烯烃与苯硼酸进行Suziku偶联的反应体系，并对这三个反应体系的机理进行了研究推测。通过本项目的实施，扩展了烯烃上碳氟键的活化体系，较系统地理解该类碳氟键的活化机理，为设计更有效、更广泛的碳氟键的金属催化体系积累了经验，并提供理论基础和科学依据。此外，在完成原计划研究目标的同时，还进行了含氟化合物的合成方法学研究。