芳基化合物和醌类衍生物的选择性碳氢活化研究

发布时间：2018-03-29 06:46

本文选题：碳氢活化　切入点：过渡金属催化　出处：《江南大学》2017年硕士论文

【摘要】：过渡金属催化的碳氢活化是近些年有机合成界的重要研究领域。醌类化合物及其衍生物具有多样的潜在药用价值,因而研究它们的合成方法具有重要的意义。本文主要研究过渡金属催化的含氮基团导向的芳基化合物的选择性碳氢活化和醌类衍生物的碳氢活化。这些研究可以在一定程度上推动导向的芳基化合物的选择性碳氢活化的研究进展,同时也为一些以芳基醌类及含硫芳基醌类衍生物为中间体的药物合成提供新思路。主要内容如下:1、铑催化的酰胺导向的选择性碳氢活化烯基化反应的研究发展了以[Cp*RhCl_2]_2为催化剂,以碳酸银为氧化剂的二芳基酰胺的选择性碳氢活化反应。该方法加入三氟甲烷磺酸银来辅助催化剂催化,可以选择性生成酰胺N-芳环一侧的产物;而不加时则生成C-芳环一侧的环化产物。本文报道的酰胺的烯基化反应具有很好的化学和区域选择性以及官能团耐受性。机理探索实验证明非配阴离子在该反应中起了一个关键作用,并提出了可能的反应机理。2、铑催化的酰胺导向的选择性碳氢活化酰胺基化反应的研究发展了一种全新的使用过渡金属铑催化酰胺与异氰酸酯选择性碳氢活化酰胺化反应合成不对称酰胺的方法。此类反应条件简单,同时有着良好到优秀的产率。反应对各种异氰酸烷基酯都适用,甚至异氰酸芳基酯也能参与反应。该方法提供了一种高效且实用的不对称双酰胺的合成方法。3、铑催化的三唑导向的选择性碳氢活化烯基化反应的研究设计了一种吡啶基苯并三唑类化合物来研究与丙烯酸酯类化合物的选择性碳氢活化偶联反应。反应以[Cp*RhCl_2]_2为催化剂,醋酸铜为氧化剂,六氟锑酸银为添加剂展开,结果发现碳氢活化能够选择性的发生在吡啶环上,说明在这一类化合物中三唑基的导向能力要大于吡啶基。此外,我们发现各种带供电子基团或者吸电子基团的苯基苯并三唑类化合物均可以得到良好到优秀收率的产物。此外,我们也对该反应做了一系列的机理探索实验。4、铜催化的苯醌与苯磺酰氯类化合物偶联生成含硫芳基醌类衍生物的研究首次采用苯磺酰氯作为偶联试剂,在廉价的CuI催化和还原剂三苯基磷的帮助下与苯醌偶联选择性地生成含硫芳基醌类衍生物,而无其他磺酰基醌类衍生物生成。各种单取代和双取代的苯磺酰氯都能以中等到良好的产率得到目标产物。这为含硫芳基醌类衍生物的合成提供了一种新选择。5、钯催化的萘醌、卤代苯酚及卤代烷烃三组分交叉偶联为芳基醌类衍生物的研究拓展了一种醋酸钯催化的合成芳基醌类衍生物的方法,采用碘代苯酚及卤代烷烃与萘醌三组分一锅法交叉偶联来合成。其中,卤代烷烃既是反应物又是溶剂。与前人的合成方法相比,该方法具有操作简单、条件温和、绿色经济等突出优点。
[Abstract]:Hydrocarbon activation catalyzed by transition metals is an important research field in the field of organic synthesis in recent years. Quinones and their derivatives have a variety of potential medicinal value. In this paper, the selective hydrocarbon activation of nitrogen-oriented aryl compounds catalyzed by transition metals and the hydrocarbon activation of quinone derivatives are studied. Promote to some extent the research progress of selective hydrocarbon activation of oriented aryl compounds, It also provides a new idea for the synthesis of aryl quinones and sulfur-containing aryl quinones derivatives as intermediates. The main contents are as follows: 1, Rhodium catalyzed amide-oriented selective hydrocarbon activation alkylation reaction developed with [Cp*RhCl_2] 2 as catalyst, The selective hydrocarbon activation reaction of diaryl amides with silver carbonate as oxidant. Silver trifluoromethane sulfonic acid was added to assist the catalyst to selectively produce the product of N-aromatic ring of amide. The alkenylation reaction of amides reported in this paper has good chemical and regioselectivity and functional group tolerance. The mechanism exploration experiments have proved that non-ligand anions are present in this reaction. Played a key role, The possible reaction mechanism. 2. Rhodium catalyzed amide-oriented selective hydrocarbon activation amidation reaction has developed a novel transition metal rhodium catalyzed amide and isocyanate selective hydrocarbon activated amide. A method for the synthesis of asymmetric amides by chemical reactions. The conditions for such reactions are simple, At the same time have good to excellent yield. The reaction is applicable to all kinds of isocyanate alkyl ester, Even aryl isocyanate can take part in the reaction. This method provides an efficient and practical method for the synthesis of asymmetric bisamides. Rhodium catalyzed triazole-oriented selective hydrocarbon activation alkylation reaction has been designed. The selective hydrocarbon activation coupling reaction of acrylates with pyridyl benzo triazole compounds was studied. [Cp*RhCl_2] 2 was used as catalyst. Copper acetate is used as oxidant and silver hexafluoroantimonate as additive. The results show that hydrocarbon activation can selectively occur on pyridine ring, indicating that the guiding ability of triazole group in this kind of compounds is greater than that of pyridine group. It has been found that all kinds of phenyl benzo triazole compounds with or without electron groups can be obtained in good yields. We have also done a series of experiments on the mechanism of this reaction. 4. The coupling of benzoquinone catalyzed by copper with benzenesulfonyl chloride derivatives to form sulfur-containing aryl quinone derivatives was studied for the first time using benzenesulfonyl chloride as coupling reagent. Aryl quinone derivatives containing sulfur were selectively synthesized by coupling with benzoquinone with the help of cheap CuI catalysis and triphenyl phosphorus reductant. However, no other sulfonyl quinone derivatives were formed. All kinds of monosubstituted and disubstituted benzenesulfonyl chloride could obtain the target product in medium to good yield. This provides a new choice for the synthesis of sulfur-containing aryl quinone derivatives. 5, palladium catalyzed naphthoquinone, Studies on Cross-Coupling of three components of Halogenated Phenol and Halogenated hydrocarbons to aryl Quinone Derivatives A method for Synthesis of aromatic Quinone Derivatives catalyzed by Palladium Acetate was extended. The method of cross-coupling of iodophenol and halogenated hydrocarbon with naphthoquinone in one pot is used. Halogenated hydrocarbons are both reactants and solvents. Compared with the previous synthesis method, this method is simple in operation and mild in conditions. Green economy and other outstanding advantages.
【学位授予单位】：江南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

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