3,4,6-tri-O-benzyl-2-deoxy-2-(phenylthio)-β-D-glucose | 117901-42-5

• 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: 3,4,6-tri-O-benzyl-2-deoxy-2-(phenylthio)-β-D-glucose
• 英文别名: 3,4,6-Tri-O-benzyl-2-deoxy-2-phenylthio-α-D-glucopyranose；2-deoxy-3,4,6-tri-O-benzyl-2-thiophenyl-α-D-galacto-pyranose；3,4,6-tri-O-benzyl-2-deoxy-2-phenylthio-D-galactose；2-deoxy-3,4,6-tri-O-benzyl-2-thiophenyl-D-pyranose
• CAS: 117901-42-5；136174-68-0；136174-89-5；136174-91-9
• 化学式: C₃₃H₃₄O₅S
• 分子量: 542.696
• InChiKey: GCYHIZPYVVSMSC-QRUXFFLXSA-N

物化性质

• 沸点：
  687.8±55.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.25
• 重原子数：
  39.0
• 可旋转键数：
  12.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  57.15
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-benzyl-2-deoxy-2-(phenylthio)-β-D-glucose 在 molecular sieve 、 偶氮二异丁腈 、 三正丁基氢锡 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 甲苯 为溶剂， 反应 0.5h， 生成 phenyl 2-deoxy-3,4,6-tri-O-benzyl-β-D-galacto-pyranoside
  参考文献：
  名称：

  A highly stereoselective synthesis of aryl 2-deoxy-.beta.-glycosides via the Mitsunobu reaction

  摘要：

  A highly stereoselective (6.5- > 20:1) synthesis of aryl 2-deoxy-beta-D-glycosides is described. This method involves the Mitsunobu coupling of phenols and 2-alpha-(thiophenyl)- or 2-alpha-(selenophenyl)-alpha-D-pyranoses 3-6, 18, and 19 followed by Bu3SnH reduction of the PhS- and PhSe-groups.

  DOI：

  10.1021/jo00020a003
• 作为产物：
  描述：

  3,4,6-三邻苄基半乳醛 、 苯次磺酰氯 在 sodium carbonate 作用下， 生成 3,4,6-tri-O-benzyl-2-deoxy-2-(phenylthio)-β-D-glucose
  参考文献：
  名称：

  A highly stereoselective synthesis of aryl 2-deoxy-.beta.-glycosides via the Mitsunobu reaction

  摘要：

  A highly stereoselective (6.5- > 20:1) synthesis of aryl 2-deoxy-beta-D-glycosides is described. This method involves the Mitsunobu coupling of phenols and 2-alpha-(thiophenyl)- or 2-alpha-(selenophenyl)-alpha-D-pyranoses 3-6, 18, and 19 followed by Bu3SnH reduction of the PhS- and PhSe-groups.

  DOI：

  10.1021/jo00020a003

文献信息

• Wild, Robert; Schmidt, Richard R., Liebigs Annalen, 1995, # 5, p. 755 - 764
  作者：Wild, Robert、Schmidt, Richard R.

  DOI：——

  日期：——
• Studies on the Synthesis of Aureolic Acid Antibiotics: Highly Stereoselective Synthesis of Aryl 2-Deoxy-.beta.-glycosides via the Mitsunobu Reaction and Synthesis of the Olivomycin A-B Disaccharide
  作者：William R. Roush、Xiao-Fa Lin

  DOI：10.1021/ja00113a013

  日期：1995.3

  The Mitsunobu reaction of phenols and 1,2-cis-2-thiophenyl-alpha-D-glycopyranoses or 1,2-cis-2-selenophenyl-alpha-D-glycopyranoses is a very effective method for the highly stereoselective synthesis of aryl 2-deoxy-beta-D-glycosides. The equatorial 2-thiophenyl or 2-selenophenyl- substituents are easily removed by Bu(3)SnH reduction following the glycosidation reaction to provide the aryl 2-deoxy-beta-D-glycosides in good to excellent yield. The aryl beta-D-glycosides are obtained with 6.5:1 selectivity in the least selective case(Table 1) and up to >20:1 selectivity in others. The reaction appears to be S-N(2)-like in character (see 30), in that the beta:alpha reaction stereoselectivity correlates well with the alpha:beta anomeric composition of the pyranose starting material. The equatorial 2-thiophenyl or 2-selenophenyl substituents play an important role by increasing the alpha:beta anomer ratio of the pyranose starting materials. The reactions do not appear to proceed by way of free oxonium ions such as 17, since several reactions in which 17 was deliberately generated (e.g., TMS-OTf promoted reactions of glycosyl acetate 14, BF3 . Et(2)O catalyzed reactions of imidate 15) gave at best 1:1 mixtures of alpha- and beta-glycosides, and in several cases gave alpha-glycosides with >10:1 selectivity. These data also rule out the involvement of episulfonium ion 18 as a kinetically significant intermediate in reactions that proceed by way of oxonium ion 17. A short and highly effective synthesis of reducing disaccharide 53 from D-fucal was developed. This functionalized disaccharide readily undergoes Mitsunobu glycosidation with 2-naphthol, providing the model naphthyl A-B disaccharide 5 with 11:1 beta,alpha:alpha,alpha selectivity. Finally, olivin precursor 63 has also been glycosylated with 53, providing the advanced synthetic intermediate 6 with excellent diastereoselectivity.