【摘要】：黃酮類(lèi)化合物具有廣譜的藥理作用,因而越來(lái)越引人矚目。然而某些黃酮類(lèi)化合物在天然植物中的含量普遍偏低,且分離提取困難,嚴(yán)重阻礙了對(duì)這些化合物后續(xù)的活性研究。FlavumounesB、CalodeninA、CalodeninB是類(lèi)含有苯并呋喃結(jié)構(gòu)的黃酮類(lèi)化合物,在自然界中分布均較少,且無(wú)文獻(xiàn)報(bào)道相關(guān)的化學(xué)合成路線。本文共嘗試了三種合成策略來(lái)合成這三種天然黃酮類(lèi)化合物的關(guān)鍵中間體。第一種合成策略嘗試是以芹菜素為起始原料,經(jīng)選擇性保護(hù)、碘代、sonogashira反應(yīng)、選擇性脫保護(hù)、羰基插入、氫化等一系列反應(yīng),以及數(shù)次的保護(hù)基調(diào)整以后,成功得到了側(cè)環(huán)未氫化的FlavumounesB合成中間體。第二種合成策略嘗試合成CalodeninB,本文成功得到了2-取代-3-羰基苯并呋喃結(jié)構(gòu)的合成中間體。第三種合成策略采用1, 3-二羰基化合物與2, 4, 6-三羥基苯乙酮為底物,通過(guò)氧化加成反應(yīng)一步構(gòu)建了 2-取代-3-羰基苯并呋喃結(jié)構(gòu),經(jīng)過(guò)多次嘗試,我們最終得到了 CalodeninB的同分異構(gòu)體。此外本論文還研究了保護(hù)基對(duì)羰基插入反應(yīng)的影響以及不同底物脫乙�；Ｗo(hù)基的反應(yīng)條件。本文成功合成目標(biāo)天然黃酮類(lèi)化合物Flavumounes B、Calodenin A、CalodeninB的數(shù)個(gè)關(guān)鍵中間體化合物,且通過(guò)對(duì)這三種不同的合成策略的嘗試,提示我們要避免使用空間位阻比較大的保護(hù)基,同時(shí)又要考慮底物的結(jié)構(gòu)對(duì)氫化反應(yīng)的影響,這部分工作為將來(lái)合成該類(lèi)化合物提供參考。
[Abstract]:Flavonoids have attracted more and more attention because of their broad-spectrum pharmacological effects. However, the content of some flavonoids in natural plants is generally low, and it is difficult to separate and extract them. FlavumounesB, Calodenin A, Calodenin B are flavonoids containing benzofuran structure. Three synthetic strategies have been tried to synthesize the key intermediates of these three natural flavonoids. The first synthetic strategy is based on apigenin as the starting material, selective protection, iodide, Sonogashira reaction, and selective deactivation. A series of reactions, such as protection, carbonyl insertion, hydrogenation, and several modifications of the protective groups, were successfully used to synthesize flavumounesB. The second synthetic strategy was to synthesize CalodeninB, and the 2-substituted-3-carbonyl benzofurans were successfully synthesized. The structure of 2-substituted-3-carbonyl benzofurans was constructed by one-step oxidation-addition reaction of carbonyl compounds with 2,4,6-trihydroxyacetophenone. After several attempts, the isomers of Calodenin B were obtained. In addition, the effect of protective groups on carbonyl insertion reaction and deacetylation protection of different substrates were also studied. Several key intermediates of target natural flavonoids Flavumounes B, Calodenin A and Calodenin B have been successfully synthesized in this paper. Attempts to synthesize these three key intermediates suggest that we should avoid using a protective radical with large steric hindrance and consider the structure of substrates for hydrogenation. This work will provide references for the future synthesis of the compounds.
【學(xué)位授予單位】：天津科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：R914

【參考文獻(xiàn)】

相關(guān)期刊論文 前4條

1 劉曉平;于小鳳;洪秀云;郅慧;黃二芳;胡春;;黃酮衍生物的合成及其抗炎活性研究[J];中國(guó)藥物化學(xué)雜志;2009年05期

2 張紀(jì)寧;楊潔;;黃酮類(lèi)化合物的生物活性研究進(jìn)展[J];伊犁師范學(xué)院學(xué)報(bào)(自然科學(xué)版);2009年02期

3 延璽;劉會(huì)青;鄒永青;任占華;;黃酮類(lèi)化合物生理活性及合成研究進(jìn)展[J];有機(jī)化學(xué);2008年09期

4 王瑋,王琳;黃酮類(lèi)化合物的研究進(jìn)展[J];沈陽(yáng)醫(yī)學(xué)院學(xué)報(bào);2002年02期

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本文編號(hào)：2196199