phenyl 3,4,6-tri-O-acetyl-2-deoxy-2-fluoro-1-thio-β-D-mannopyranose | 1320281-48-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 3,4,6-tri-O-acetyl-2-deoxy-2-fluoro-1-thio-β-D-mannopyranose
• 英文别名: phenyl 3,4,6-tri-O-acetyl-2-deoxy-2-fluoro-1-thio-α-D-mannopyranoside uronate
• CAS: 1320281-48-8
• 化学式: C₁₈H₂₁FO₇S
• 分子量: 400.425
• InChiKey: XBAPMIIPROBARI-ILOCAZANSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.27
• 重原子数：
  27.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  88.13
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  phenyl 3,4,6-tri-O-acetyl-2-deoxy-2-fluoro-1-thio-β-D-mannopyranose 在 甲醇 、 2,2,6,6-四甲基哌啶氧化物 、 碘苯二乙酸 、 sodium methylate 、 sodium hydride 、 potassium carbonate 、 对甲苯磺酸 作用下， 以 甲醇 、 水 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 9.0h， 生成
  参考文献：
  名称：

  Mannopyranosyl Uronic Acid Donor Reactivity

  摘要：

  The reactivity of a variety of mannopyranosyl uronic acid donors was assessed In a set of competition experiments, in which two (S)-tolyl mannosyl donors were made to compete for a limited amount of promoter (NIS/TfOH). These experiments revealed that the reactivity of mannuronic acid donors is significantly higher than expected based on the electron-withdrawing capacity of the C-5 carboxylic acid ester function. A 4-O-acetyl-beta-(S)-tolyl mannuronic acid donor was found to have similar reactivity as per-O-benzyl-alpha-(S)-tolyl mannose.

  DOI：

  10.1021/ol2016862
• 作为产物：
  描述：

  1,3,4,6-tetra-O-acetyl-2-deoxy-2-fluoromannopyranose 在 氢溴酸 、 sodium hydride 作用下， 以 二氯甲烷 、 溶剂黄146 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 5.0h， 生成 phenyl 3,4,6-tri-O-acetyl-2-deoxy-2-fluoro-1-thio-β-D-mannopyranose
  参考文献：
  名称：

  Mannopyranosyl Uronic Acid Donor Reactivity

  摘要：

  The reactivity of a variety of mannopyranosyl uronic acid donors was assessed In a set of competition experiments, in which two (S)-tolyl mannosyl donors were made to compete for a limited amount of promoter (NIS/TfOH). These experiments revealed that the reactivity of mannuronic acid donors is significantly higher than expected based on the electron-withdrawing capacity of the C-5 carboxylic acid ester function. A 4-O-acetyl-beta-(S)-tolyl mannuronic acid donor was found to have similar reactivity as per-O-benzyl-alpha-(S)-tolyl mannose.

  DOI：

  10.1021/ol2016862

文献信息

• Oxidative Activation of C–S Bonds with an Electropositive Nitrogen Promoter Enables Orthogonal Glycosylation of Alkyl over Phenyl Thioglycosides
  作者：Annabel Kitowski、Ester Jiménez-Moreno、Míriam Salvadó、Jordi Mestre、Sergio Castillón、Gonzalo Jiménez-Osés、Omar Boutureira、Gonçalo J. L. Bernardes

  DOI：10.1021/acs.orglett.7b02886

  日期：2017.10.6

  method for the selective activation of thioglycosides that uses the N+-thiophilic reagent O-mesitylenesulfonylhydroxylamine (MSH) as a promoter is presented. The reaction proceeds via anomeric mesitylensulfonate intermediates, which could be isolated and fully characterized by placing a fluorine atom at the C2 position. In the presence of a soft Lewis acid, glycosylation reaction proceeds at ambient temperature

  提出了一种选择性活化硫糖苷的方法，该方法使用N +-亲硫试剂O-均三甲苯磺酰基羟胺（MSH）作为促进剂。该反应通过异戊基均磺酸磺酸盐中间体进行，该中间体可以被分离并且可以通过将氟原子置于C 2位来充分表征。在软路易斯酸的存在下，糖基化反应在环境温度下以良好的产率进行。进一步证明，在S-苯基供体的存在下可以正交活化S-乙基，从而可以设计顺序糖基化策略。