平分型N-糖链的合成方法研究及应用
摘要
恶性肿瘤是严重威胁人类生命和生活质量的主要疾病。时至今日,尚未完全揭示出恶性肿瘤的原因和机理,也未能研制发明出治愈恶性肿瘤的理想方法和药物。已有证据表明,平分型N-糖链在某些肿瘤细胞中降低了肿瘤细胞的转移率。虽然这种结论现在还不是十分的明确,但这对人们在寻找如何抑制肿瘤细胞的转移提供了一条很有前途的道路。研究平分型N-糖链在肿瘤细胞的转移方面起到怎样的生物信息功能必将为抗肿瘤药物的研究提供新的靶点和思路。本论文完成了具有复杂结构的平分型N-糖链的合成方法研究并对其中的新方法进行推广应用:1、将羟基异构化的方法应用于合成塔罗糖及其乙酰化衍生物,发现一条高效简洁的新路线。2、将首次发现的苄叉基保护的葡萄糖原酸酯策略成功应用于葡萄糖2,3位羟基的选择性区分。
一、平分型N-糖链的合成方法学研究
1、通过设计并合成化合物模型M1,确定了先连接1→3分支,再连接1→4分支,最后连接1→6分支的平分型N-糖链三分支糖链的连接顺序问题以及在连接过程中需要注意的问题,解决了合成平分型N-糖链中的第一个难点。
2、先后尝试了采用甘露糖基供体直接构建法,氧化还原法, SN2亲核反应法三种方法构建含有β-甘露糖苷键的糖基片段。最后通过分子内SN2亲核反应法找到了一条高效构建N-糖链核心三糖的新路线,这也是迄今已报道的最简洁高效的路线。解决了合成平分型N-糖链中最为关键的第二个难点。
3、以简洁的合成路线完成平分型N-糖链三分支片断B、C、D的合成。其中糖基供体片断B、D为首次合成,为平分型N-糖链的合成完成了砌块的构建
4、采用砌块式合成策略分别以总步骤49步,最长线性步骤33步,最长线性收率5.2%和总步骤48步,最长线性步骤32步,最长线性收率6.5%完成两种平分型N-糖链的合成。
二、塔罗糖及其乙酰化衍生物的合成研究了以廉价易得的半乳糖为原料,经过简单高效的3步反应,高产率的得到塔罗糖及其乙酰化衍生物的新路线。两个塔罗糖的乙酰化衍生物可作为手性源进行其它化合物的合成,有机合成提供了新的廉价手性原料。
三、苄叉基保护的葡萄糖原酸酯的合成及应用研究
1、通过设计三种不同的4,6苄叉基保护的硫苷供体与甲醇生成原酸酯,通过对3位羟基进行转保护基操作然后进行原酸酯水解,得到2,3位选择性保护的葡萄糖片段,解决了葡萄糖2,3位羟基选择性区分的一大难点。
2、发现了苄叉基保护的原酸酯高效生成的条件,并且发现氯代亚甲基-4,6-O-苄叉基原酸酯比其它形式的原酸酯稳定。通过培养氯代亚甲基-4,6-O-苄叉基原酸酯两种构型的单晶,并通过X衍射分析其在空间上的构象。
Cancer is a class of diseases which endangers human life and quality of life. Until now, the mechanism of cancer has not been illuminated, nor has the ideal method and drug to cure cancer. It has been suggested that bisecting N-glycans depress the metastasis of cancer. Although this conclusion has not been clearly identified, it may become a valuable approach to depress cancer metastasis. The research on the bioinformation function of bisecting N-glycans on cancer metastasis will provide a new target for anti-cancer drug. This research accomplished the synthesis of complicated bisecting N-glycans and extended the application of the new method: 1. Finding a new highly convenient route of D-talose synthesis and its acetylation derivates by hydroxy epimerization; 2. Protecting 2,3-dihydroxyl groups ofβ-D-glucopyranoside regioselectively by applying the new 4,6-O-benzylidene- protected-1,2-orthoesters strategy.
Study on Synthesis N-Glycans of the Bisecting Type
1 Though design and synthesis of compound model M1, the connection sequence problem of three branch of bisecting N-glycans was solved by connecting the 1→3 branch first, then the 1→4 branch, and 1→6 branch finally. As a result, the first choke for the synthesis of bisecting N-glycans was solved.
2. The fragment withβ-D-mannoside was synthesized by directβ-D-mannoside coupling method, oxidation/reduction method and SN2 inversion method in sequence. A new highly convenient route for the core trisaccharide of N-glycans construction was found by the SN2 inversion method. And it is the most convenient route which has been reported until now. The second choke point for the synthesis of bisected N-glycans was resolved.
3. Three substituent fragments of bisecting N-glycans-Compound B, Compound C and Compound D were synthesized. Among them, Compound B and Compound D were synthesized for the first time.
4. Though adopting the tactic of convergent block synthesis, this paper synthesized two bisecting N-glycans with 49 steps in total, 5.2% yield for 33 steps in filiform, and 48 steps in total, 6.5% yield for 32 steps in filiform.
Synthesis of Talose and its Acetylation Derivates
A new route for the synthesis of talose and its acetylation derivates was found by 3 steps using galactose as starting material. And two acetylation derivates of talose could be used as starting chiral reagents for other compounds. Study on the Synthesis of 4,6-O-Benzylidene-protected-1,2-orthoesters and Its
Application.
1. Three types of 4,6-O-benzylidene-protected-thioglycoside were designed to react with methanol to give orthoesters. Then the orthoesters were hydrolyzed after the protecting group of OH-3 was converted to other protecting group. As a result, the glycosyl fragment with 2,3 hydroxyls protected by different groups was obtained. In this section, the choke point for regioselective protection of 2,3 hydroxyls of glucoside was resolved.
2. We found the reaction requirement for the synthesis of 4,6-O-benzylidene -protected-1,2-orthoesters. Moreover, we discovered that chloromethyl-4,6-O- benzylidene-protected-1,2-orthoesters were more stable than other types. Though obtaining two types of monocrystal configuration for 4,6-O-benzylidene- protected-1,2-orthoesters and analyzing the conformation of the monocrystal using single crystal diffraction.
一、平分型N-糖链的合成方法学研究
1、通过设计并合成化合物模型M1,确定了先连接1→3分支,再连接1→4分支,最后连接1→6分支的平分型N-糖链三分支糖链的连接顺序问题以及在连接过程中需要注意的问题,解决了合成平分型N-糖链中的第一个难点。
2、先后尝试了采用甘露糖基供体直接构建法,氧化还原法, SN2亲核反应法三种方法构建含有β-甘露糖苷键的糖基片段。最后通过分子内SN2亲核反应法找到了一条高效构建N-糖链核心三糖的新路线,这也是迄今已报道的最简洁高效的路线。解决了合成平分型N-糖链中最为关键的第二个难点。
3、以简洁的合成路线完成平分型N-糖链三分支片断B、C、D的合成。其中糖基供体片断B、D为首次合成,为平分型N-糖链的合成完成了砌块的构建
4、采用砌块式合成策略分别以总步骤49步,最长线性步骤33步,最长线性收率5.2%和总步骤48步,最长线性步骤32步,最长线性收率6.5%完成两种平分型N-糖链的合成。
二、塔罗糖及其乙酰化衍生物的合成研究了以廉价易得的半乳糖为原料,经过简单高效的3步反应,高产率的得到塔罗糖及其乙酰化衍生物的新路线。两个塔罗糖的乙酰化衍生物可作为手性源进行其它化合物的合成,有机合成提供了新的廉价手性原料。
三、苄叉基保护的葡萄糖原酸酯的合成及应用研究
1、通过设计三种不同的4,6苄叉基保护的硫苷供体与甲醇生成原酸酯,通过对3位羟基进行转保护基操作然后进行原酸酯水解,得到2,3位选择性保护的葡萄糖片段,解决了葡萄糖2,3位羟基选择性区分的一大难点。
2、发现了苄叉基保护的原酸酯高效生成的条件,并且发现氯代亚甲基-4,6-O-苄叉基原酸酯比其它形式的原酸酯稳定。通过培养氯代亚甲基-4,6-O-苄叉基原酸酯两种构型的单晶,并通过X衍射分析其在空间上的构象。
Cancer is a class of diseases which endangers human life and quality of life. Until now, the mechanism of cancer has not been illuminated, nor has the ideal method and drug to cure cancer. It has been suggested that bisecting N-glycans depress the metastasis of cancer. Although this conclusion has not been clearly identified, it may become a valuable approach to depress cancer metastasis. The research on the bioinformation function of bisecting N-glycans on cancer metastasis will provide a new target for anti-cancer drug. This research accomplished the synthesis of complicated bisecting N-glycans and extended the application of the new method: 1. Finding a new highly convenient route of D-talose synthesis and its acetylation derivates by hydroxy epimerization; 2. Protecting 2,3-dihydroxyl groups ofβ-D-glucopyranoside regioselectively by applying the new 4,6-O-benzylidene- protected-1,2-orthoesters strategy.
Study on Synthesis N-Glycans of the Bisecting Type
1 Though design and synthesis of compound model M1, the connection sequence problem of three branch of bisecting N-glycans was solved by connecting the 1→3 branch first, then the 1→4 branch, and 1→6 branch finally. As a result, the first choke for the synthesis of bisecting N-glycans was solved.
2. The fragment withβ-D-mannoside was synthesized by directβ-D-mannoside coupling method, oxidation/reduction method and SN2 inversion method in sequence. A new highly convenient route for the core trisaccharide of N-glycans construction was found by the SN2 inversion method. And it is the most convenient route which has been reported until now. The second choke point for the synthesis of bisected N-glycans was resolved.
3. Three substituent fragments of bisecting N-glycans-Compound B, Compound C and Compound D were synthesized. Among them, Compound B and Compound D were synthesized for the first time.
4. Though adopting the tactic of convergent block synthesis, this paper synthesized two bisecting N-glycans with 49 steps in total, 5.2% yield for 33 steps in filiform, and 48 steps in total, 6.5% yield for 32 steps in filiform.
Synthesis of Talose and its Acetylation Derivates
A new route for the synthesis of talose and its acetylation derivates was found by 3 steps using galactose as starting material. And two acetylation derivates of talose could be used as starting chiral reagents for other compounds. Study on the Synthesis of 4,6-O-Benzylidene-protected-1,2-orthoesters and Its
Application.
1. Three types of 4,6-O-benzylidene-protected-thioglycoside were designed to react with methanol to give orthoesters. Then the orthoesters were hydrolyzed after the protecting group of OH-3 was converted to other protecting group. As a result, the glycosyl fragment with 2,3 hydroxyls protected by different groups was obtained. In this section, the choke point for regioselective protection of 2,3 hydroxyls of glucoside was resolved.
2. We found the reaction requirement for the synthesis of 4,6-O-benzylidene -protected-1,2-orthoesters. Moreover, we discovered that chloromethyl-4,6-O- benzylidene-protected-1,2-orthoesters were more stable than other types. Though obtaining two types of monocrystal configuration for 4,6-O-benzylidene- protected-1,2-orthoesters and analyzing the conformation of the monocrystal using single crystal diffraction.
引文
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