缺电子炔烃参与的1,3-偶极环加成反应研究

发布时间：2018-03-22 06:28

本文选题：吡咯并[3　切入点：4-c]吡咯　出处：《扬州大学》2017年硕士论文　论文类型：学位论文

【摘要】：1,3-偶极环加成反应具有分子多样性、区域选择性和立体选择性等特点,近年来得到了有机化学家的广泛关注。缺电子炔烃能与含氮亲核试剂形成活性偶极中间体,继而发生1,3-偶极环加成和Diels-Alder等反应,在有机合成中的应用越来越广泛。本文主要研究了以α-氨基酸与缺电子炔烃合成的新型1,3-偶极子为合成子,进行1,3-偶极环加成反应,合成了一系列结构新颖的吡咯衍生物和螺环吡咯烷衍生物。1、研究了乙醇溶剂中,α-氨基酸、丁炔二酸二酯和N-取代马来酰亚胺三组分合成吡咯并[3,4-c]吡咯衍生物的反应。不同结构的氨基酸,产物的构型有所不同,表现出丰富的分子多样性和高非对映选择性。该反应具有原料简单易得、反应条件温和、操作简便等优点,为结构复杂的稠合吡咯环衍生物的合成提供了便利方法。所合成的39个化合物均通过IR、1HNMR、13CNMR、HRMS等方法进行了结构表征,并对其中6个典型化合物进行了单晶结构的表征。2、研究了乙醇溶剂中,α-氨基酸、丁炔二酸二酯与2-芳亚甲基-1,3-茚满二酮的三组分1,3-偶极环加成反应,产物为结构新颖的官能化的螺环吡咯烷衍生物。所合成的32个未经报道的化合物均通过IR、1HNMR、13CNMR、HRMS等方法进行了结构表征,并对其中5个典型化合物进行了单晶结构的表征。3、研究了乙腈溶剂中,氨基酸和丁炔二酸二酯参与的多组分合成多取代吡咯或吡咯嗪衍生物的串联反应。该反应中,丁炔二酸二酯既与氨基酸发生加成反应生成偶极中间体,又作为亲偶极体参与到反应中。共合成了 15个未经报道的吡咯或吡咯嗪衍生物,均通过IR、1HNMR、13CNMR、HRMS等方法进行了结构表征,并对其中4个典型化合物进行了单晶结构的表征。
[Abstract]:Due to its molecular diversity, regioselectivity and stereoselectivity, 1H _ 3-dipolar cycloaddition reaction has been widely concerned by organic chemists in recent years. Electron deficient alkynes can form active dipolar intermediates with nitrophilic reagents. In this paper, the synthesis of 伪 -amino acids with electron-deficient alkynes as synthesizer is mainly studied, in which a new type of 1H _ 3- dipole is used as synthesizer to carry out 1 ~ (3) -dipolar cycloaddition reaction, which is a new type of synthesis of 伪 -amino acids and electron-deficient alkynes, and is used in the synthesis of 伪 -amino acids and electron-deficient alkynes. A series of novel pyrrole derivatives and spirocyclic pyrrolidine derivatives. The synthesis of pyrrolidone [3Py _ 4-c] pyrrole derivatives from succinylenedioic acid diester and N-substituted maleimide. The configuration of the product is different with different amino acids. The reaction shows rich molecular diversity and high enantioselectivity. The reaction has the advantages of simple and easy to obtain raw materials, mild reaction conditions, easy operation, and so on. It provides a convenient method for the synthesis of polypyrrole ring derivatives with complex structure. All the 39 compounds synthesized were characterized by IR 1HN MR13 CNMR-HRMS, etc. Six typical compounds were characterized by single crystal structure. The reaction of 伪 -amino acids, diesters of succinylenedioate and 2-arylene methylenedione with 3-indene 3-dipolar cycloaddition in ethanol solvent was studied. The products were novel functionalized spirocyclic pyrrolidine derivatives. The 32 unreported compounds were characterized by IR 1H NMR13 CNMR-HRMS. Five typical compounds were characterized by single crystal structure. The series reaction of polysubstituted pyrrole or pyrrolidine derivatives was studied in acetonitrile solvent, in which amino acids and succinylenediester were involved in the synthesis of polysubstituted pyrrole or pyrrolidine derivatives. The dipolar intermediates were formed by addition reaction of succinylenedioate with amino acids, and were also involved as dipolar bodies. Fifteen unreported pyrrole or pyrrolidine derivatives were synthesized and characterized by IR 1H NMR 13CNMRHRMS. Four typical compounds were characterized by single crystal structure.
【学位授予单位】：扬州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25

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