质子酸催化的烯丙基亚胺离子分子内环化反应

发布时间：2018-03-27 09:59

本文选题：质子酸　切入点：亚胺离子　出处：《兰州交通大学》2017年硕士论文

【摘要】：本论文研究了质子酸催化的烯丙基亚胺离子分子内环化反应,主要包括以下三章内容:第一章:简述了(1)质子酸催化剂催化反应的历程(2)质子酸催化剂的发展前景(3)亚胺离子中间体在环化反应中的应用。第二章:三氟乙酸催化的烯丙基亚胺离子环化构建环戊并[b]吲哚骨架反应研究。环戊并[b]吲哚骨架广泛存在于天然产物和药物分子中,含有环戊并[b]吲哚骨架结构的化合物具有抗肿瘤、抗菌、杀虫等功效,由此可见,发展高效构建环戊并[b]吲哚骨架的方法具有重要意义。本课题发展的三氟乙酸催化吲哚取代烯丙基亚胺离子分子内环化反应构建吲哚衍生物目前尚未见其它报道。反应过程中,由于催化剂TFA具有吸湿发烟、腐蚀性,所以采用硅胶负载;而且生成水为唯一副产物。该方法不仅丰富了质子酸催化剂在催化合成中的应用,而且为吲哚衍生物的合成提供了研究基础。第三章:PPA催化的烯丙基亚胺离子环化构建茚类衍生物反应研究。茚环骨架是许多天然产物的核心骨架,广泛存在于生物活性分子、功能材料和过渡金属络合物中,其中金属-茚基配合物在催化烯烃聚合中具有显著效果,因此,合成茚类衍生物具有重要意义。多磷酸(PPA)是一种强无机酸,具有较强的脱水性能,广泛用于分子内和分子间酰化,杂环合成和酸催化反应中。本课题提供了一种独特的、新颖的PPA催化烯丙基亚胺离子中间体采用外型关环模式构建茚环骨架的方法。该反应具有以下优点:原料便宜易得、底物普适性好(不仅适用于富电子体系,对于缺电子醛也很有效)、无金属参与、原子经济性高。本课题为合成茚烷衍生物提供了良好的研究基础。
[Abstract]:In this paper, the intramolecular cyclization of allyl imines catalyzed by proton acid was studied. The main contents are as follows: chapter 1: the course of catalytic reaction of proton acid catalyst 2) the prospect of proton acid catalyst) the application of imine ion intermediate in cyclization reaction. Chapter 2: trifluoroacetic acid. Cyclization of Allyl imines to Cyclopentazo [b] Indole cytoskeleton. Cyclopentazo [b] indole cytoskeleton is widely present in natural products and drug molecules. Compounds containing cyclopentyl [b] indole skeleton have anti-tumor, antibacterial and insecticidal properties. It is of great significance to develop an efficient method for the construction of cyclization of cyclization of cyclization of cyclization of cyclization of cyclization of indole-substituted allyl imide ion with trifluoroacetic acid. Because the catalyst TFA is hygroscopically smoky and corrosive, it is supported by silica gel and water is the only by-product. This method not only enriches the application of proton acid catalyst in catalytic synthesis. It also provides a basis for the synthesis of indole derivatives. Chapter 3: PPA catalyzed cyclization of allyl imines to indene derivatives. Indenyl cytoskeleton is the core skeleton of many natural products and widely exists in bioactive molecules. In functional materials and transition metal complexes, the metal-indenyl complexes have remarkable effect in catalytic olefin polymerization, so the synthesis of indene derivatives is of great significance. It is widely used in intramolecular and intermolecular acylation, heterocyclic synthesis and acid-catalyzed reactions. A novel PPA catalytic method for the construction of indene cytoskeleton in allyl imide ion intermediates using external ring closure mode is presented. The reaction has the following advantages: the raw material is cheap and easy to obtain, the substrate is universal (not only suitable for electron-rich systems, but also suitable for electronic systems). For the lack of electron aldehydes is also very effective, no metal participation, high atomic economy. This topic provides a good basis for the synthesis of ninhydrin derivatives.
【学位授予单位】：兰州交通大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.256.9

【参考文献】