β-硫代糖苷的合成方法研究及晶体结构表征  

Synthesis and Crystal Structure Characterization ofβ-Thioglycoside

作　　者：华敏 熊涛 陈绍彦 曹燕来 姚辉 黄年玉 刘明国 HUA Min;XIONG Tao;CHEN Shao-yan;CAO Yan-lai;YAO Hui;HUANG Nian-yu;LIU Ming-guo(Key Laboratory of Natural Products Research and Development,College of Biological and Pharmaceutical Sciences,China Three Gorges University,Yichang 443002,China;Hubei Guangchen Pharmaceutical Co.,Ltd.,Yichang 443002,China)

机构地区：[1]三峡大学生物与制药学院天然产物研究与利用湖北省重点实验室,湖北宜昌443002 [2]湖北广辰药业股份有限公司,湖北宜昌443002

出　　处：《化学试剂》2022年第8期1233-1240,共8页Chemical Reagents

基　　金：国家自然科学基金项目(82003621);湖北省科技厅自然科学基金项目(2020CFB205);湖北省教育厅自然科学基金项目(Q20201204);高等学校学科创新引智计划项目(No.D20015)。

摘　　要：通过化学方法非对映选择性合成β-硫代糖苷,并对其进行结构分析。以三乙酰基葡萄烯糖为起始原料,经过水解、缩合、酯化后得到葡萄烯糖-3-吡啶酸酯,筛选了钴催化下其与苯亚磺酸钠反应的最佳条件,合成系列β-硫代糖苷衍生物,分析产物的立体化学结构。以三乙酰基葡萄烯糖为起始原料经4步反应合成β-硫代糖苷,总产率为42%~46%;通过X-射线单晶衍射分析出(4a R,6 S,8a S)-6-((4-氯苯基)硫代)-2-(4-甲氧基苯基)-4,4a,6,8a-四氢吡喃[3,2-d][1,3]二噁英的Flack参数为0.002(6)。方法使用廉价金属催化剂,无毒无臭,操作简便,为β-硫代糖苷的研究提供理论依据和基础。β-thioglycosides were diastereoselectively synthesized by chemical methods,and their structures were analyzed.The picoloylglucal donor was obtained by hydrolysis,condensation,and esterification from the starting material of commercial tri-O-acetyl-D-glucal.After screening the optimized reaction conditions of picoloylglucal donor and sodium benzene sulfinate,a series ofβ-thioglycosides was synthesized under the catalysis of cobalt.Then the stereochemical structures of the products were characterized.Theβ-thioglycosides were synthesized with a total yield of 42%~46%by four-step reaction using tri-O-acetyl-D-glucal as the starting material,and(4aR,6S,8aS)-6-((4-chlorophenyl)thio)-2-(4-methoxyphenyl)-4,4a,6,8a-tetrahydropyrano[3,2-d][1,3]dioxine was analyzed by X-ray crystallography with a Flack parameter of 0.002(6).This simple methodology using cheap,nontoxic,and odorless metal catalysts would provide a theoretical basis for the study ofβ-thioglycosides.

关 键 词：钴催化 硫糖苷 合成 晶体结构 α-葡萄糖苷酶抑制活性 

分 类 号：R914.5[医药卫生—药物化学]