發(fā)布時(shí)間：2018-03-16 05:27

  本文選題：烯烴關(guān)環(huán)復(fù)分解　切入點(diǎn)：釕卡賓　出處：《昆明理工大學(xué)》2017年碩士論文　論文類(lèi)型：學(xué)位論文

【摘要】：大位阻烯烴復(fù)分解反應(yīng)是釕催化烯烴復(fù)分解研究中尚未解決的問(wèn)題。在天然產(chǎn)物和活性藥物分子的合成中,常因位阻影響無(wú)法應(yīng)用烯烴復(fù)分解反應(yīng)。此外,即使對(duì)于能夠構(gòu)建的大位阻反應(yīng)體系,也仍存在反應(yīng)活性低、催化劑用量大、立體化學(xué)難以控制等問(wèn)題。因此,大位阻烯烴復(fù)分解反應(yīng)研究具有重要的理論和應(yīng)用價(jià)值。在本論文中,我們?cè)噲D借助氫鍵的促進(jìn)作用實(shí)現(xiàn)大位阻烯烴關(guān)環(huán)復(fù)分解反應(yīng)。首先綜述了近二十年來(lái)在氫鍵促進(jìn)烯烴復(fù)分解反應(yīng)方面的進(jìn)展,隨后對(duì)我們近來(lái)在三取代、四取代大位阻烯烴關(guān)環(huán)復(fù)分解方面的研究工作分別進(jìn)行了總結(jié),然后對(duì)反應(yīng)中釕雜質(zhì)的除去方法進(jìn)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,發(fā)展了一類(lèi)HG-II催化、烯丙位羥基促進(jìn)的三取代關(guān)環(huán)復(fù)分解反應(yīng),系統(tǒng)地研究了該反應(yīng)的反應(yīng)條件、底物普適性,并通過(guò)計(jì)算和對(duì)照實(shí)驗(yàn)提出了可能的反應(yīng)機(jī)理。2.在氫鍵促進(jìn)的三取代烯烴關(guān)環(huán)復(fù)分解研究中,發(fā)現(xiàn)此類(lèi)關(guān)環(huán)復(fù)分解反應(yīng)可用于合成四取代的目標(biāo)雙鍵,并對(duì)反應(yīng)的底物范圍進(jìn)行了探索。3.在上述烯烴關(guān)環(huán)復(fù)分解反應(yīng)研究過(guò)程中,發(fā)現(xiàn)反應(yīng)中HG-II分解產(chǎn)生多種含釕雜質(zhì),難以通過(guò)柱層析除去。經(jīng)反復(fù)嘗試,發(fā)現(xiàn)乙二胺類(lèi)試劑能夠有效與含釕雜質(zhì)反應(yīng),建立了一類(lèi)簡(jiǎn)便易行的反應(yīng)后處理方法,并對(duì)此方法的通用性進(jìn)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.
【學(xué)位授予單位】：昆明理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O621.25

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本文編號(hào)：1618544