S-phenyl 2,3,4-tri-O-benzyl-6,6-difluoro-α-D-thiorhamnopyranoside | 953817-83-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: S-phenyl 2,3,4-tri-O-benzyl-6,6-difluoro-α-D-thiorhamnopyranoside
• 英文别名: (2S,3S,4S,5S,6R)-2-(difluoromethyl)-3,4,5-tris(phenylmethoxy)-6-phenylsulfanyloxane
• CAS: 953817-83-9
• 化学式: C₃₃H₃₂F₂O₄S
• 分子量: 562.677
• InChiKey: LJWJOGBQXLHHKE-VDYFTJCESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  40
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  62.2
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  S-phenyl 2,3,4-tri-O-benzyl-6,6-difluoro-α-D-thiorhamnopyranoside 、 双丙酮半乳糖 在 3 A molecular sieve 三氟甲磺酸酐 作用下， 以 二氯甲烷 为溶剂， 以57%的产率得到2,3,4-tri-O-benzyl-6,6-difluoro-β-D-rhamnopyranosyl-(1->6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose
  参考文献：
  名称：

  Synthesis and Glycosylation of a Series of 6-Mono-, Di-, and Trifluoro S-Phenyl 2,3,4-Tri-O-benzyl-thiorhamnopyranosides. Effect of the Fluorine Substituents on Glycosylation Stereoselectivity

  摘要：

  A series of 6-mono-, di-, and trifluoro analogs of S-phenyl 2,3,4-tri-O-benzyl-D- or L-thiorhamnopyranoside has been synthesized and used as donors in glycosylation reactions, with activation by the 1-benzenesulfinyl pipe ridine/triflic anhydride system. The stereochemical outcome of the glycosylation reactions was found to depend on the electron-withdrawing capability of the disarming substituent at the 6-position, i.e., on the number of fluorine atoms present. The results are explained with regard to the increased stability of the glycosyl triflates, shown to be intermediates in the reaction by low-temperature H-1 NMR experiments, with increased fluorine content.

  DOI：

  10.1021/ja0730258
• 作为产物：
  描述：

  acetyl 2,3,4-tri-O-benzyl-6,6-difluoro-D-rhamnopyranoside 、 苯硫酚 在 吡啶 、 三氟甲磺酸三甲基硅酯 、 3 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 生成 S-phenyl 2,3,4-tri-O-benzyl-6,6-difluoro-α-D-thiorhamnopyranoside 、 S-phenyl 2,3,4-tri-O-benzyl-6,6-difluoro-β-D-thiorhamnopyranoside
  参考文献：
  名称：

  Synthesis and Glycosylation of a Series of 6-Mono-, Di-, and Trifluoro S-Phenyl 2,3,4-Tri-O-benzyl-thiorhamnopyranosides. Effect of the Fluorine Substituents on Glycosylation Stereoselectivity

  摘要：

  A series of 6-mono-, di-, and trifluoro analogs of S-phenyl 2,3,4-tri-O-benzyl-D- or L-thiorhamnopyranoside has been synthesized and used as donors in glycosylation reactions, with activation by the 1-benzenesulfinyl pipe ridine/triflic anhydride system. The stereochemical outcome of the glycosylation reactions was found to depend on the electron-withdrawing capability of the disarming substituent at the 6-position, i.e., on the number of fluorine atoms present. The results are explained with regard to the increased stability of the glycosyl triflates, shown to be intermediates in the reaction by low-temperature H-1 NMR experiments, with increased fluorine content.

  DOI：

  10.1021/ja0730258

文献信息

• Synthesis and Glycosylation of a Series of 6-Mono-, Di-, and Trifluoro <i>S</i>-Phenyl 2,3,4-Tri-<i>O</i>-benzyl-thiorhamnopyranosides. Effect of the Fluorine Substituents on Glycosylation Stereoselectivity
  作者：David Crich、Olga Vinogradova

  DOI：10.1021/ja0730258

  日期：2007.9.1

  A series of 6-mono-, di-, and trifluoro analogs of S-phenyl 2,3,4-tri-O-benzyl-D- or L-thiorhamnopyranoside has been synthesized and used as donors in glycosylation reactions, with activation by the 1-benzenesulfinyl pipe ridine/triflic anhydride system. The stereochemical outcome of the glycosylation reactions was found to depend on the electron-withdrawing capability of the disarming substituent at the 6-position, i.e., on the number of fluorine atoms present. The results are explained with regard to the increased stability of the glycosyl triflates, shown to be intermediates in the reaction by low-temperature H-1 NMR experiments, with increased fluorine content.