本文選題：石松生物堿 + Lycopalhine�。� 參考：《山西師范大學(xué)》2017年碩士論文

【摘要】：Palhinine類生物堿是近年來我國(guó)不同科研小組從不同產(chǎn)地的石松中分離出的具有籠狀立體結(jié)構(gòu)的一類石松生物堿。因?yàn)槠浣Y(jié)構(gòu)復(fù)雜性,國(guó)內(nèi)外已有多個(gè)課題組參與其合成競(jìng)爭(zhēng)。Lycopalhine A作為Palhinine類石松生物堿中結(jié)構(gòu)最為復(fù)雜的一個(gè),含有9個(gè)手性碳原子,其中有8個(gè)連續(xù)相鄰;另外,分子中的8個(gè)單環(huán)結(jié)構(gòu)形成了復(fù)雜的籠狀結(jié)構(gòu)。Lycopalhine A在天然石松中含量極低,分離提純的樣品不足滿足其生物活性篩選。因此簡(jiǎn)潔高效的全合成方法就顯得尤為重要。本論文的主要工作集中在Lycopalhine A關(guān)鍵中間體烯酮衍生物合成及其結(jié)構(gòu)鑒定方面。分別在非手性和手性條件下完成了關(guān)鍵中間體烯酮衍生物外消旋體和左、右旋體的合成,還對(duì)其中涉及的Pauson-Khand反應(yīng)進(jìn)行了系統(tǒng)的方法學(xué)研究。新穎手性炔烴化合物也是合成Lycopalhine A的關(guān)鍵中間體。對(duì)其進(jìn)行手性分離及光學(xué)純度測(cè)定具有非常重要的意義。由于結(jié)構(gòu)中的炔基、烯基及烷基不是很好的固定相,且炔基和烯基并不是一個(gè)很好的紫外生色團(tuán),所以無法直接通過手性柱HPLC進(jìn)行分離、分析。而利用制備HPLC衍生化反應(yīng)需要繁瑣的檢測(cè)過程。本論文發(fā)展了一種使用手性HPLC法通過分離、分析手性炔烴鈷配合物方法測(cè)定炔烴化合物的光學(xué)純度新方法。設(shè)計(jì)利用手性炔烴化合物炔基原位與Co2(CO)8配位生成穩(wěn)定的手性Co2(CO)6-aIkyne配合物,通過對(duì)該配合物進(jìn)行液相分離、分析,間接測(cè)定了原手性炔烴化合物的光學(xué)純度。該方法適用范圍,廣泛適用于沒有經(jīng)典生色團(tuán)的炔烴類化合物。
[Abstract]:Palhinine alkaloids are a kind of Chinese pine alkaloids with cage solid structure which were isolated from different producing areas by different research groups in China in recent years. Because of its complex structure, many domestic and foreign research groups have participated in the synthesis competition. Lycopalhine A is the most complicated one of the alkaloids of Palhinine pine, which contains 9 chiral carbon atoms, 8 of which are adjacent to each other. The complex cage structure, Lycopalhine A, was formed in 8 monocyclic structures of the molecule, and the content of Lycopalhine A in natural pine was very low. The samples isolated and purified could not satisfy the screening of biological activity. Therefore, a simple and efficient total synthesis method is particularly important. The main work of this thesis is focused on the synthesis and structure identification of Lycopalhine A key intermediate ketene derivatives. The synthesis of racemes, left and right racemes of key intermediate ketene derivatives was carried out under the condition of non-chiral and chiral respectively, and the Pauson-Khand reactions involved in them were systematically studied. Novel chiral alkynes are also the key intermediates in the synthesis of Lycopalhine A. Chiral separation and optical purity determination are of great significance. Because the alkynyl, alkyl and alkyl in the structure are not very good stationary phase, and the alkyl and alkyl are not a good UV chromophore, they can not be separated and analyzed directly by chiral column HPLC. However, the preparation of HPLC derivative reaction requires a tedious detection process. In this paper, a new method for the determination of optical purity of alkynes by chiral HPLC method is developed. The chiral alkynes were designed to coordinate with Co2(CO)8 in situ to form a stable chiral Co2(CO)6-aIkyne complex. The optical purity of the chiral alkynes was determined indirectly by liquid phase separation and analysis. The method is widely applied to alkynes without classical chromophore.
【學(xué)位授予單位】：山西師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.3

【參考文獻(xiàn)】

相關(guān)期刊論文 前3條

1 陳業(yè)高;劉怡君;蔣金和;劉波;;石松類生物堿成分研究的新進(jìn)展[J];云南師范大學(xué)學(xué)報(bào)(自然科學(xué)版);2010年06期

2 袁珊琴,欒新慧;石松生物堿成分的研究進(jìn)展[J];軍事醫(yī)學(xué)科學(xué)院院刊;1999年01期

3 程源深,呂傳真,應(yīng)智林,倪望云,張慈祿,桑國(guó)衛(wèi);石杉?jí)A甲治療重癥肌無力癥128例[J];新藥與臨床;1986年04期

，

本文編號(hào)：1830154