高价碘介导的芳基偶联及重排反应：一种合成联芳基化合物的新方法

发布时间：2018-12-28 15:40

【摘要】：联芳基化合物是一类重要的结构单元，已被发现存在于一些具有药理活性的天然产物中，同时在有机反应中也有着重要的应用。近年来两芳环的直接脱氢偶联反应成为了构建联芳基化合物的一个新的策略。该方法具有原子经济性以及绿色环保等优点，因此也备受有机化学研究者的关注。现有的方法绝大数都需要过渡金属的参与，而且还存在一些底物局限性以及反应温度高等问题。本文介绍了一种由高价碘试剂介导的脱氢偶联及重排反应制备联芳基化合物的方法，该反应包括如下特点：1）芳环C(sp2)与芳环C(sp2)键的形成；2）芳环C(sp2)与酰胺C(O)键的断裂；3）内酰胺化或内酯化。我们以2-酰胺基苯甲酰胺类化合物119为底物，以PIDA（二乙酰氧基碘苯）为氧化剂在乙腈中回流反应，共制备了21个具有潜在药理活性的联芳基化合物121；以2-羟基苯甲酰胺类化合物132为底物，二氯甲烷为溶剂，在PIFA/BF3·OEt2（双三氟乙酰氧基碘苯/三氟化硼乙醚）的作用下，通过一锅法制备了17个具有新型结构的联芳基化合物133。所有的产物都进行了氢谱、碳谱、红外及质谱表征，产物121a还通过单晶衍射的方法进行了结构确证。同时我们还提出了该重排反应的可能机理，中间体134的发现以及部分实验事实证明了该机理的合理性。除此之外，我们还对产物的应用进行了初步的探索，通过对部分产物的水解，我们得到了非对称结构同时还具有氨基、羟基官能团的联芳基化合物。
[Abstract]:Diaryl compounds are important structural units, which have been found in some natural products with pharmacological activities, and also have important applications in organic reactions. In recent years, direct dehydrogenation of two aromatic rings has become a new strategy for the construction of biaryl compounds. This method has many advantages, such as atomic economy and green environmental protection, so it has attracted much attention of organic chemistry researchers. Most of the existing methods require transition metals, and there are some problems such as substrate limitation and high reaction temperature. In this paper, a method for preparing biaryl compounds by dehydrogenation coupling and rearrangement mediated by high valence iodine reagents is introduced. The reaction includes the following characteristics: 1) the formation of the bond between aromatic ring C (sp2) and aromatic ring C (sp2); 2) the cleavage of aromatic ring C (sp2) with amide C (O) bond, 3) lactam or internal esterification. A total of 21 biaryl compounds with potential pharmacological activities were prepared by reflux reaction in acetonitrile with 2-aminobenzamide (119) as substrate and PIDA (diacetyl iodobenzene) as oxidant. Using 2-hydroxybenzoamide compound 132 as substrate, dichloromethane as solvent, under the action of PIFA/BF3 OEt2 (bisfluoroacetyl iodiobenzene / boron trifluoride ether), Seventeen diaryl compounds with new structure were prepared by one pot method. All the products were characterized by hydrogen spectrum, carbon spectrum, IR and MS, and the structure of product 121a was confirmed by single crystal diffraction. At the same time, the possible mechanism of the rearrangement reaction was proposed, and the discovery of intermediate 134 and some experimental facts proved the rationality of the mechanism. In addition, we also explored the application of the product. By hydrolysis of some of the products, we obtained the asymmetric structure with amino, hydroxyl functional groups of the biaryl compounds.
【学位授予单位】：天津大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：R914.5

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