摘要共轭二烯是一大类重要的有机化合物,它在天然产物和药物活性分子中大量出现。通过C-H键活化的烯烃直接交叉偶联反应合成共轭二烯的方法存在很多优点，该方法不仅合成效率高，而且解决了烯烃的预先活化和副产物多的问题。近年来，对于Csp2-H键活化反应的研究方兴日盛，但这类反应大多需要外加过量的氧化剂来完成催化循环。如果使用氧化型导向基，也就是在导向基中引入某些特殊的基团充当内氧化剂，就能避免外加氧化剂带来的环境污染，简化反应体系，提高反应效率。62391

本论文主要围绕过渡金属催化的氧化型导向碳氢键活化反应开展研究，主要内容包括: 采用酰胺基团既作为导向基又作为分子内的氧化剂,在温和的反应条件下,实现了铑催化的丙烯酰胺与醋酸烯丙酯的氧化偶联反应, 高选择性得到了1,3-二烯类化合物。我们优化了催化反应条件，探究了不同的溶剂、温度、氧化剂等对催化反应的影响，并在最优条件下合成了若干新型的官能化1,3 -丁二烯衍生物，具有很重要的合成应用价值。相信随着该烯烃交叉偶联反应研究的不断深入，该类反应在有机合成中将会发挥更大的作用。

毕业论文关键词：碳氢键活化；钌催化；酰胺基导向；氧化型导向基 

Abstract Conjugated diene represents a large class of important natural products and pharmaceutically active compounds. Cross-coupling reaction between alkenes by vinylic C-H bond activation not only exhibits high efficiency toward the synthesis of conjugated olefins, but also it obviates prefunctionaliztion steps and minimizes waster formation. In recent years, many efforts have been focused on the application of the Csp2-H bond activation. However, these transformations usually require excess amount of external oxidants to oxidize low valent metal and regenerate the active catalytic species. The use of the oxidizing directing group, which contains some special group acting as the internal oxidant, can avoid the troubles arousing from the external oxidants and make the reaction process more simple and efficient.

This dissertation mainly focused on the studies of the oxidizing directing group C-H bond activation, the contents are as following: we used amide group as an oxidizing directing group , Under mild reaction conditions, the oxidative coupling reaction of acrylamide with allyl acetate catalyzed by ruthenium or rhodium, high selective synthesis of 1,3- diene compounds were obtained. We screened different solvents, temperatures and oxidants and optimized reaction conditions. Several functionalized 1,3-butadienes were obtained successfully by this catalytic conditions. With the research gets further, it is believed that this reaction will play a great role in organic synthesis .

Key words: C-H bond activation; ruthenium-catalyzed; acylamino directed; oxidizing directing group

一．引言 4

1.1 共轭二烯化合物的重要性及其传统的合成方法 4

1.2过渡金属催化下官能团导向的烯烃间偶联反应 6

1.3 利用氧化型导向基的优点 9

1.4本研究课题的意义 11

二．实验部分 12

2.1 实验仪器 12

2.2实验试剂 13

2.3 烯烃底物的制备 13

2.3.1实验步骤A：从酰氯与胺合成相应的丙烯酰胺 13

2.3.2实验步骤B：从酸合成相应的丙烯酰胺 14

2.4条件优化