Carlsberg Laboratory , 10 Gamle Carlsberg Vej, 1799 Copenhagen V, Denmark.
J Nat Prod. 2016 Apr 22;79(4):1198-202. doi: 10.1021/acs.jnatprod.5b01121. Epub 2016 Mar 9.
An effective method for the chemical synthesis of cyanogenic glucosides has been developed as demonstrated by the synthesis of dhurrin, taxiphyllin, prunasin, sambunigrin, heterodendrin, and epiheterodendrin. O-Trimethylsilylated cyanohydrins were prepared and subjected directly to glucosylation using a fully acetylated glucopyranosyl fluoride donor with boron trifluoride-diethyl etherate as promoter to afford a chromatographically separable epimeric mixture of the corresponding acetylated cyanogenic glucosides. The isolated epimers were deprotected using a triflic acid/MeOH/ion-exchange resin system without any epimerization of the cyanohydrin function. The method is stereocontrolled and provides an efficient approach to chemical synthesis of other naturally occurring cyanogenic glucosides including those with a more complex aglycone structure.
已开发出一种有效的氰基葡萄糖苷的化学合成方法，如通过合成野靛碱、荭草苷、原矢车菊苷、山萮菜苷、异山萮菜苷和表异山萮菜苷得到证实。用全乙酰化的葡萄糖氟化物供体和三氟化硼-二乙醚作为促进剂，将 O-三甲基硅基氰醇直接进行糖苷化，得到相应的乙酰化氰基葡萄糖苷的可分离的非对映异构体混合物。使用三氟甲磺酸/甲醇/离子交换树脂体系对分离得到的非对映异构体进行脱保护，氰醇官能团没有发生任何差向异构化。该方法具有立体选择性，为其他天然存在的氰基葡萄糖苷的化学合成提供了一种有效的方法，包括那些具有更复杂糖苷配基结构的氰基葡萄糖苷。
