卟琳铁催化的基于亲电试剂捕捉活性铵基叶立德中间体的反应研究

发布时间：2018-03-08 15:29

本文选题：铁卡宾　切入点：氨　出处：《华东师范大学》2017年博士论文　论文类型：学位论文

【摘要】：作为地壳中含量最多的过渡金属,铁具有廉价、安全等优势。利用铁催化来代替贵重金属催化成为合成化学家关注的焦点之一。虽然铁催化分解重氮的反应自上世纪90年代才被发现,并且这方面的研究报道较少。铁催化剂在催化卡宾转移反应中已经表现出非常好的催化性能,铁的配合物可以与重氮形成铁卡宾,进而发生一系列的转化,如环丙烷化反应,插入反应等。在已有的报道中,螺环双VA唑啉配体与铁形成的配合物在不对称O-H插入反应中取得了非常优异的对映选择性。同时,卟啉铁在N-H插入过程中表现出非常好的选择性控制。本论文主要围绕将铁催化应用于多组分反应中以及相关机理的研究。论文的第一章前言介绍了铁卡宾、亲电试剂捕捉活性叶立德和离子对活性中间体的多组分反应以及氨在有机合成中的应用等内容。同时,对该论文的研究思路也做了介绍。论文的第二章的研究首次实现了对于重氮和脂肪胺形成的铵基叶立德的捕捉的三组分反应。反应的成功实现证明了脂肪胺的插入反应经过了叶立德过程并且该反应提供了高效合成β-羟基α-氨基酸酯结构的方法。论文的第三章实现了亲电试剂靛红对于重氮和氨形成的叶立德捕捉过程,实现了利用廉价易得的工业原料氨合成高附加值一级胺的反应。该过程具有非常好的化学选择性。并且通过控制实验我们发现产物的位阻效应决定了反应的化学选择性。论文的第四章的研究是对于反应机理的探究,我们合成并且通过单晶结构表征了吸电子基团铁卡宾结构,这是首例吸电子取代铁卡宾晶体的报道。并且我们首次实现了合成出来的铁卡宾对于胺的N-H插入过程,证明了卟啉铁催化的N-H插入反应经过了卡宾中间体过程。同时我们还实现了吸电子铁卡宾与苯胺形成的叶立德的亲电捕捉过程,证明了三组分反应过程也经历了铁卡宾中间体过程。论文第五章的研究是无金属催化的重氮的卤代反应。该反应可用于高效构建3-卤代氧化吲哚结构和烯基卤代物。该反应具有非常好的普适性,我们顺利实现了重氮酰胺的氟代,氯代,溴代和碘代。我们还实现了 3-溴代氧化吲哚的克级规模合成。
[Abstract]:As the most abundant transition metal in the earth's crust, iron is cheap. Safety and other advantages. The use of iron instead of precious metal catalysis has become one of the focuses of synthetic chemists. Although iron catalyzed decomposition of diazo was only discovered in -10s, Iron catalysts have shown very good catalytic performance in the carbene transfer reaction. Iron complexes can form tecabine with diazo and then undergo a series of transformations, such as cyclopropanation. In previous reports, the complexes formed by spirocyclic bis (VA) azoline ligands with iron obtained excellent enantioselectivity in asymmetric O-H insertion reactions. Porphyrin iron shows very good selective control during N-H insertion. In this paper, the application of iron catalyst in multicomponent reactions and related mechanisms are studied. The electrophilic reagents capture the multicomponent reaction of active Ylide and ion-pair active intermediates and the application of ammonia in organic synthesis. In the second chapter, the capture reaction of ammonium ylide formed by diazo and aliphatic amine was realized for the first time. The successful realization of the reaction proved the insertion of aliphatic amine. The entry reaction went through the Ylide process and provided an efficient method for the synthesis of 尾 -hydroxyl 伪 -amino acid esters. In chapter 3, the electrophilic reagent indirubin was used to capture the formation of diazo and ammonia. The synthesis of high value-added amine from ammonia, a cheap and easily available industrial raw material, has been realized. This process has very good chemical selectivity. By controlling the experimental results, we find that the reaction chemistry is determined by the steric resistance effect of the product. Selectivity. Chapter 4th of the paper is devoted to exploring the mechanism of the reaction. We have synthesized and characterized the structure of the ircarbene group by single crystal structure, which is the first report of the substitution of the electron absorption group for the iron carbene crystal, and we have realized the N-H insertion process of the synthesized iron carbene for amine for the first time. It is proved that the N-H intercalation reaction catalyzed by iron porphyrin has gone through the carbene intermediate process, and we have also realized the electrophilic trapping process of Ylide formed by the formation of iron carbene and aniline. It has been proved that the three component reaction process also experienced the intermediate process of iron carbene. Chapter 5th is a metal-free diazo halogenation reaction. This reaction can be used to efficiently construct the structure of 3-halogenated indoles and alkenyl halogenates. The reaction is very general, We have successfully achieved the fluorination, chlorination, bromination and iodization of diazoamides.
【学位授予单位】：华东师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O621.251

【相似文献】