(2R,3R,5R,6R)-3,5-Bis-benzyloxy-2-ethylsulfanyl-6-methyl-tetrahydro-pyran | 172361-29-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,3R,5R,6R)-3,5-Bis-benzyloxy-2-ethylsulfanyl-6-methyl-tetrahydro-pyran
• 英文别名: (2R,3R,5R,6R)-2-ethylsulfanyl-6-methyl-3,5-bis(phenylmethoxy)oxane
• CAS: 172361-29-4
• 化学式: C₂₂H₂₈O₃S
• 分子量: 372.529
• InChiKey: KDUIDBBRSAMDHF-BRKWEVRTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  53
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2R,3R,5R,6R)-3,5-Bis-benzyloxy-2-ethylsulfanyl-6-methyl-tetrahydro-pyran 在 palladium on activated charcoal N-碘代丁二酰亚胺 、 氢气 、 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 、 溶剂黄146 、 甲苯 为溶剂， 反应 0.83h， 生成 (1S,3R,4R,5S,6R,7R,20R,22S,23S,24R)-23-((2R,3R,5R,6R)-3,5-Dihydroxy-6-methyl-tetrahydro-pyran-2-yloxy)-22-methoxy-2,9,18,21,25-pentaoxa-tricyclo[18.2.2.1^3,7]pentacosane-4,5,6,24-tetraol
  参考文献：
  名称：

  拴系三糖的合成，以探讨糖-蛋白相互作用中糖间的柔性。

  摘要：

  三糖表位的两个晶体结构alpha-D-Galp（1-> 2）[alpha-D-Abep（1-> 3）alpha-D-Manp1-> OCH（3）1与抗体Fab和单链Fv片段已用于指导分子内束缚的设计，该束缚将三糖配体约束为接近结合态的构象。配体的预组织应克服对结合的熵罚并提供增强的亲和力。使用三个系链[O（CH（2））（n）（）O，n = 6、7和8]固定甘露糖和半乳糖残基的溶剂暴露C6原子。使用了两种合成方案。第一种使用带有被保护为三苯甲基醚6-8的系链的1-硫代半乳糖苷乙基。供体6-8中的任何一个在C6处含有甲磺酸盐的甘露吡喃糖苷5的糖基化得到二糖37-39。随后除去三苯甲基，允许在系链的ω-羟基上生成醇盐，以38％的收率置换磺酸盐。通过比较，当掺入ω-甲磺酰氧基系绳作为甘露糖苷9时，与半乳糖基供体10反应后的二糖产物52以61％的产率转化为大环4。通过硫代糖苷化学法引入3，6-二脱氧

  DOI：

  10.1021/jo9806097
• 作为产物：
  描述：

  溴甲苯 、 Ethyl 3,6-dideoxy-1-thio-D-xylo-hexopyranoside 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 Ethyl 2,4-di-O-benzyl-3,6-dideoxy-1-thio-β-D-xylo-hexopyranoside 、 (2R,3R,5R,6R)-3,5-Bis-benzyloxy-2-ethylsulfanyl-6-methyl-tetrahydro-pyran
  参考文献：
  名称：

  Synthesis of a Pentasaccharide Epitope for the Investigation of Carbohydrate-Protein Interactions

  摘要：

  Pyranose residues of a polysaccharide that are not involved in the principal sugar-protein antibody combining site, filled by trisaccharide 1, cause a 50-fold reduction in intrinsic affinity. The antibody is crystallographically characterized, and the residue responsible for the lost binding energy has been identified as the terminal disaccharide Rha-->Gal of pentasaccharide 5. This disaccharide segment of 5 may avoid protein contact by adopting the ''anti'' conformer about the preceding Man-Rha glycosidic linkage. Monosaccharide thioglycoside synthons 6-9 were used in NIS-promoted glycosylations to synthesize the pentasaccharide as a glycoside that was suitable for binding and solution conformational studies. Disaccharide 29 was obtained upon the addition of rhamnose building unit 6 to the (trimethylsilyl)ethyl galactopyranoside 10 followed by protecting group manipulation. The sequential addition of 7-9 to 29 afforded the pentasaccharide derivative 35 bearing a 2-O-benzoate group suited for subsequent 1,2-trans-glycoside synthesis following its conversion to a glycosyl imidate. In order to preserve the integrity of the 3,6-dideoxyhexopyranosyl glycosidic bond during cleavage of the (trimethylsilyl)ethyl group leading to the imidate 39, it was essential to convert the benzylated pentasaccharide target 35 into its fully acylated derivative 37. Pentasaccharide 5 was obtained by transesterification of the protected glycoside 40 formed via 39. Qualitative NOE measurements suggest a predominant solution conformation for 5 that cannot be adopted in the bound state due to protein-oligosaccharide clashes at the periphery of the binding site.

  DOI：

  10.1021/jo00127a043