钯催化的卤代芳烃与富电子烯烃的区域选择性Heck反应研究.pdf

钯催化的卤代芳烃与富电子烯烃的区域选择性 Heck 反应研究 中文摘要 Heck偶联反应是形成碳碳键的最有力工具，而卤代芳烃与富电子烯烃的Heck芳 基化反应的区域选择性非常差一直是阻碍其广泛应用的关键原因，也是最近十几 年来的研究热点。为了克服这个问题，我们开发了几个新的催化体系，使很多富 电子烯烃的 Heck 芳基化反应的区域选择性得到了明显改善。主要内容和结果如 下：（1）使用季铵盐作添加剂，在异丙醇中高选择高产率实现了N-乙酰基-N-乙 烯基胺的 Heck 芳基化偶联反应。（2）纯水作溶剂，季铵盐作添加剂，高选择高 产率实现了多种富电子烯烃的Heck芳基化偶联反应（3）乙二醇作溶剂，无需任 何添加剂，Pd（OAc）2 作催化剂，DPPF 作配体，高选择高产率得到了各类芳基 酮类化合物。 关键词： 钯催化剂 富电子烯烃 Heck反应 区域选择性 3 钯催化的卤代芳烃与富电子烯烃的区域选择性 Heck 反应研究 英文摘要 The Heck reaction is one of the most powerful tools for constructing the new C-C bonds.But the poor arylation regio-selectivity of electron-rich olefins with the aryl halides has hampered its application,and this has been a hot topic during the last more than ten years.To overcome this problem,we have developped several new catalytic systems,which have greatly improved the regio-selectivity of many electron-rich olefins. The main contents are as follows: (1) In the presence of hydrogen-bond donor salt [H NiPr ][BF ] as an additive, a new highly efficient protocol for 2 2 4 the Pd-catalyzed regio-selective Heck arylation of the electron-rich olefin N-acyl-N-vinylamine with aryl halides has been developed. The reaction proceeds smoothly in isopropanol to afford exclusively the branched products in high yields.(2) In the presence of hydrogen-bond donor salt [H NiPr ][BF ] as an additive, highly regio-selective Heck 2 2 4 arylation of electron-rich olefins by aryl halides has been achieved in water.(3)A new method has been developped which allows various aryl ketones were synthesized by coupling of aryl halides with electron-rich olefins in ethylene glycol at 145℃ wi