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

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.