寡糖糖脂巯基双十六烷基醚聚乙二醇寡糖双亲性物合成方法研究  

Synthesis Method of Oligosaccharide Lipid Mercapto Dihexadecyl Ether Polyethylene Glycol Oligosaccharides

作　　者：郑海富 夏勋荣 顾佳雨 李明明 夏炎 ZHENG Haifu;XIA Xunrong;GU Jiayu

机构地区：[1]江苏省计量科学研究院(江苏省能源计量数据中心)苏州实验室,苏州215121 [2]江苏省计量科学研究院(江苏省能源计量数据中心)电离辐射与医学工程计量研究所,南京210023

出　　处：《科技创新与应用》2023年第33期18-21,共4页Technology Innovation and Application

基　　金：江苏省市场监督管理局科研项目(J2022011)。

摘　　要：该文提供两亲性含巯基双十六烷基醚聚乙二醇间链寡糖糖脂的合成方法,解决糖基供体卤代糖的稳定性差、不易保存、不易获得具有潜在药用价值糖苷化试剂的问题。利用制备获得关键中间体2,3,4,6-O-乙酰基-α-D-吡喃甘露糖三氯乙酰亚胺酯与烯丙氧基三甘醇在氯过氧苯甲酸(MCPBA)和三甲硅基三氟甲磺酸脂(TMSOTf)作为催化剂的系列反应中合成环氧丙基三甘醇酰基甘露糖。此甘露糖衍生物与十六烷基醇、三苯基十七烷基甲磺酸盐相继混合,以氢化钠为强碱条件,以三氟化硼合乙醚(BF_(3)·C_(2)H_(6)O)及碘化四丁基铵(TABI)为催化剂,合成得到三苯双十六烷基聚乙二醇甘露糖。最后,在超强碱钠块条件下与三氟乙酸(TFA)混合,在相转移催化剂苄基三乙基氯化铵(TEBA)催化下,反应制得目标产物单巯基双十六烷基醚聚乙二醇间链寡糖糖脂。该合成方法以较温和的合成途径实现常温下结构稳定、立体选择性好的较复杂糖脂化合物的制备,终末产率达到65%,为自组装单层膜(SAM)目标分子合成创新合成方法。A method for the synthesis of amphiphilic plyethylene glycol chain oligosaccharides containing sulfhydryl bishexadecyl ether was presented,which solves the problems of poor stability,preservation and obtaining glycosylation reagent with potential medicinal value of the glycosyl donor halogenated sugar.Preparation of key intermediates 2,3,4,epoxypropyl triglycol acyl mannose was synthesized from 6-O-acetyl-α-d-pyranosyl mannose trichloroacetimide ester and allyltriethylene glycol in a series of reactions catalyzed by m-Chloroperbenzoic acid(MCPBA)and trimethylsilyl trifluoromethanesulfonate(TMSOTf).The mannose derivative was mixed with hexadecyl alcohol and triphenylheptadecylmethanesulfonate successively,and sodium hydride was used as strong base,and boron trifluoride ether(BF_(3)·C_(2)H_(6)O)and tetrabutylammonium iodide were used as catalysts to produce triphenylbishexadecyl polyethylene glycol mannose.The target product of mono-mercapto-bis-hexadecyl ether polyethylene glycol chain oligosaccharide lipid,that was prepared by mixing with trifluoroacetic acid(TFA)under the condition of super-alkaline sodium block,and the reaction was catalyzed by phase-transfer catalyst benzyl triethylammonium chloride(TEBA).The synthesis method realizes the preparation of more complex glycolipids with stable structure and good stereoselectivity at room temperature with a final yield of 65%,which is an innovative synthesis method for the target molecular synthesis of self-assembled monolayers(SAM).

关 键 词：巯基 寡糖 相转移 立体选择性 反应物 

分 类 号：O646[理学—物理化学]