本文選題：Heck反應(yīng)　切入點(diǎn)：碳苷　出處：《復(fù)旦大學(xué)》2014年碩士論文　論文類型：學(xué)位論文

【摘要】：糖類化合物盡管具有良好的生理活性,但是它們自身的一‘些缺陷限制了其成藥的可能性,其中最典型的便是氧糖苷鍵的不穩(wěn)定性,因此,碳苷的研究便顯得尤為熏要。其中,碳苷二糖不僅本身具有生理活性,而且可以作為復(fù)雜分子合成的砌塊。但是,現(xiàn)有的碳苷二糖的合成方法相當(dāng)有限,因此,發(fā)展簡潔高效的碳苷二糖的合成方法是非常有意義的。本文中,我們發(fā)展了一種通過碘代外糖烯(exo-glycal)和內(nèi)糖烯(endo-glycal)進(jìn)行Heck類型偶聯(lián)反應(yīng)生成碳苷一糖的有效方法。經(jīng)過條件優(yōu)化發(fā)現(xiàn),使用Pd(OAc)2作為催化劑、dppp作為配體、K2C03作為堿時(shí),反應(yīng)以高產(chǎn)率給出了碳苷二糖產(chǎn)物,并且具有完全的立體選擇性。進(jìn)一步,我們嘗試了將碳苷二糖作為手性合成子應(yīng)用到復(fù)雜天然產(chǎn)物的合成中。KRN7000碳苷(C-KRN7000)是一種引起廣泛興趣的免疫促進(jìn)劑,結(jié)構(gòu)中包括一個(gè)半乳糖部分和一個(gè)神經(jīng)酰胺部分,兩者通過·碳苷鍵連接；神經(jīng)酰胺部分含有三個(gè)手性中心。其合成具有一定的挑戰(zhàn)性。本課題計(jì)劃使用Suzuki-Miyaura反應(yīng)首先構(gòu)建碳苷二糖,然后打開其中一個(gè)糖環(huán),以手性池策略構(gòu)建側(cè)鏈三個(gè)手性中心。該方法與已報(bào)道方法相比,路線簡潔,并可以減少不對稱操作。目前的工作主要集中在運(yùn)用Suzuki-Miyaura反應(yīng)首先構(gòu)建碳苷二糖一步。
[Abstract]:Although carbohydrates have good physiological activity, their own defects limit the possibility of their proprietary medicines, the most typical of which is the instability of oxyglycoside bonds, so the study of carbohydrates is particularly important. Glycoside disaccharide not only has physiological activity, but also can be used as a building block for complex molecular synthesis. However, the existing methods of synthesis of carbon glycoside disaccharide are quite limited, so, It is of great significance to develop a simple and efficient method for the synthesis of carbon glycoside disaccharides. We have developed an effective method for the Heck type coupling reaction of iodide exo-glycaland endo-glycal. by optimizing the conditions, it was found that when Pd(OAc)2 was used as the catalyst, the ligand K2C03 was used as the base. The reaction gives the product of carbon glycoside disaccharide in high yield, and has complete stereoselectivity. We have tried to use carbon glycoside disaccharide as a chiral synthesizer in the synthesis of complex natural products. KRN7000 C KRN7000) is a widely interesting immune promoter with a galactose component and a ceramide part in the structure. The ceramide part contains three chiral centers. Its synthesis is challenging. We plan to use the Suzuki-Miyaura reaction to construct carbon glycoside disaccharide first, and then to open one of the sugar rings. Three chiral centers of side chain were constructed by chiral pool strategy. Compared with the reported method, this method is simple and can reduce asymmetric operation. The current work is mainly focused on the construction of one-step carbon glycoside disaccharide by using Suzuki-Miyaura reaction.
【學(xué)位授予單位】：復(fù)旦大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2014
【分類號】：R914.5

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1 陶勇峰;以Heck型反應(yīng)構(gòu)建碳苷二糖以及C-KRN7000的全合成研究[D];復(fù)旦大學(xué);2014年

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本文編號：1579886