請用此 Handle URI 來引用此文件: http://hdl.handle.net/11455/96329
標題: Concise Synthesis of Stellettoside Glycosides
簡潔合成 Stellettoside 之三醣體醣苷骨架
作者: Yu-Tung Lin
林禹彤
關鍵字: L-阿拉伯糖
鑭系金屬
正交性保護基
位置選擇性保護
Stellettosides
L-arabinose
lanthanide triflates
orthogonal protecting group
regioselective protection
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摘要: We report a highly efficient strategy to synthesize the building blocks of stellettosides B, of use for biological and medicinal structure activity studies. The synthesis of Stellettoside glycosides is a challenge due to the need of multiple synthetic steps including regioselective protection and deprotection, which is used for the keeping peracetylated sugar unit of the non-reducing end after complete deprotection. By our retrosynthetic strategy, compound 1 served as a glycosyl donor starting from L-arabinose was synthesized by our recent report,9 We developed two methods for regioselective installation of orthogonal protecting group, namely ASMB, to prepare the building blocks of 10 and 11 served as glycosyl acceptors for glycosylation. We used lanthanide triflates as catalyst to get the compound 10, and used sodium thiosulfate as catalyst to get the compound 11. Model study of glycosylation between thioglycoside 5a and PMBOH was successfully achieved to obtain the desired product. Based on our experimental results, the installation of PMB group on anomeric center can be prevented the occurrence of aglycone transfer in glycosylation. Consequently, this work is still under process.
由於 Stellettoside B1-B4 混合物對於子宮頸癌的海拉細胞 (HeLa cells) 表現出中等的細胞毒殺活性 (cytotoxic activity),其 IC50 值為 9 μM,然而文獻報導並沒有分別針對這四種化合物進行活性測試,所以並不知道這四種化合物對於海拉細胞是否具有甚麼樣的生物活性,而此化合物目前也尚未成功合成。因此,為了合成非還原端之全乙醯基醣體 Stellettoside 的三醣體骨架,本篇論文將說明我們如何利用本實驗室開發之正交性保護基策略應用在以L-阿拉伯糖為起始物來合成建構組元,與解決在合成過程中前人所沒有說明的問題,進而去合成 Stellettoside 三醣體。   在合成醣體建構組元的部分,其合成策略面臨的挑戰是如何選擇性在三號或四號位置上保護和探討選擇去保護後將非還原端之乙醯基保留下來的方法開發。本論文中,我們開發出兩種不同方法,一種是在鑭系金屬催化下選擇性在三號位置引入 ASMB 保護基,而另一種是在硫代硫酸鈉的催化下選擇性在四號位置引入 ASMB 保護基。而在其醣基化反應的部分,則是目前利用 NIS 和鑭系金屬的催化下經由醣基化反應將 PMB 成功接於醣苷予體,我們期望未來也可將其應用於建構組元與三醣體的醣基化反應。
URI: http://hdl.handle.net/11455/96329
文章公開時間: 2021-07-26
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