氢键促讲大位阻烯烃关环复分解反应研究

发布时间：2018-03-16 05:27

本文选题：烯烃关环复分解　切入点：钌卡宾　出处：《昆明理工大学》2017年硕士论文　论文类型：学位论文

【摘要】：大位阻烯烃复分解反应是钌催化烯烃复分解研究中尚未解决的问题。在天然产物和活性药物分子的合成中,常因位阻影响无法应用烯烃复分解反应。此外,即使对于能够构建的大位阻反应体系,也仍存在反应活性低、催化剂用量大、立体化学难以控制等问题。因此,大位阻烯烃复分解反应研究具有重要的理论和应用价值。在本论文中,我们试图借助氢键的促进作用实现大位阻烯烃关环复分解反应。首先综述了近二十年来在氢键促进烯烃复分解反应方面的进展,随后对我们近来在三取代、四取代大位阻烯烃关环复分解方面的研究工作分别进行了总结,然后对反应中钌杂质的除去方法进行了研究,主要工作包括:1.在前期自溶霉素的全合成工作中,发展了一类HG-II催化、烯丙位羟基促进的三取代关环复分解反应,系统地研究了该反应的反应条件、底物普适性,并通过计算和对照实验提出了可能的反应机理。2.在氢键促进的三取代烯烃关环复分解研究中,发现此类关环复分解反应可用于合成四取代的目标双键,并对反应的底物范围进行了探索。3.在上述烯烃关环复分解反应研究过程中,发现反应中HG-II分解产生多种含钌杂质,难以通过柱层析除去。经反复尝试,发现乙二胺类试剂能够有效与含钌杂质反应,建立了一类简便易行的反应后处理方法,并对此方法的通用性进行了研究。
[Abstract]:Large steric hindrance olefin double decomposition is an unsolved problem in ruthenium catalyzed olefin double decomposition. In the synthesis of natural products and active drug molecules, it is often impossible to apply olefin multiple decomposition reaction due to the influence of steric hindrance. Even for the large steric resistance reaction system which can be constructed, there are still some problems such as low reaction activity, large amount of catalyst, and difficult to control stereochemistry, etc. The study of large steric hindrance olefin double decomposition reaction has important theoretical and practical value. In this paper, we try to realize the double decomposition reaction of olefin by hydrogen bond. Firstly, we review the progress of hydrogen bond in promoting the double decomposition of olefin in the last 20 years, and then we replace it in three places recently. In this paper, the research work on the double decomposition of the closed ring of tetrasubstituted large steric hindrance olefin is summarized, and the removal methods of ruthenium impurity in the reaction are studied. The main work includes: 1. In the whole synthesis of autolycin in the early stage, In this paper, a kind of HG-II catalytic and allyl hydroxyl group promoted tri-substituted closed ring double decomposition reaction was developed. The reaction conditions and substrate universality of the reaction were systematically studied. The possible reaction mechanism was put forward by calculation and control experiments. In the study of redecomposition of trisubstituted alkenes promoted by hydrogen bond, it was found that this kind of closed ring multiple decomposition reaction could be used to synthesize tetrasubstituted target double bonds. The range of substrates of the reaction was also explored. 3. During the study of the above reaction, it was found that the decomposition of HG-II resulted in a variety of ruthenium impurities, which were difficult to be removed by column chromatography. It is found that ethylenediamine reagents can react effectively with ruthenium impurity, and a kind of simple and easy post-treatment method has been established, and the generality of this method has been studied.
【学位授予单位】：昆明理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25

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