ethyl 2-deoxy-3,4,6-tri-O-acetyl-1-thio-β-D-arabino-hexopyranoside | 135824-53-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl 2-deoxy-3,4,6-tri-O-acetyl-1-thio-β-D-arabino-hexopyranoside
• 英文别名: ethyl 2-deoxy-3,4,6-tri-O-acetyl-1-thio-β-D-arabinohexopyranoside；ethyl 2-deoxy-3,4,6-tri-O-acetyl-1-thio-β-D-hexopyranoside；ethyl 2-deoxy-3,4,6-tri-O-acetyl-1-thio-arabino-hexopyranoside；[(2R,3S,4R,6S)-3,4-diacetyloxy-6-ethylsulfanyloxan-2-yl]methyl acetate
• CAS: 135824-53-2
• 化学式: C₁₄H₂₂O₇S
• 分子量: 334.39
• InChiKey: FTPWDDWCHUEJQV-MQYQWHSLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  22
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  113
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  ethyl 2-deoxy-3,4,6-tri-O-acetyl-1-thio-β-D-arabino-hexopyranoside 在 N-碘代丁二酰亚胺 、 三氟甲磺酸 、 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 2.5h， 生成 1-naphthyl 2-deoxy-α-D-arabino-hexopyranoside
  参考文献：
  名称：

  由2-脱氧-1-硫代糖苷合成芳基-2-脱氧-D-lyxo /阿拉伯糖基己吡喃糖苷。

  摘要：

  据报道由2-脱氧-1-硫代糖苷合成芳基2-脱氧-D-吡喃葡萄糖苷的任一异构体。在N-碘代琥珀酰亚胺/三氟甲磺酸存在下，当硫糖苷与不同取代的酚和萘酚反应时，α-端基异构体形成为主要产物。另一方面，首先使硫代糖苷与溴反应，然后与芳氧基阴离子反应，得到具有高特异性的芳基2-脱氧-β-D-糖苷。

  DOI：

  10.1016/j.carres.2007.02.030
• 作为产物：
  描述：

  1,3,4,6-O-四乙酰基-2-脱氧-D-吡喃葡萄糖 、 乙硫醇 在 对甲苯磺酸 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 21.0h， 生成 ethyl 2-deoxy-3,4,6-tri-O-acetyl-1-thio-β-D-arabino-hexopyranoside 、 ethyl 2-deoxy-3,4,6-tri-O-acetyl-1-thio-α-D-arabinohexopyranoside
  参考文献：
  名称：

  Erosion of Stereochemical Control with Increasing Nucleophilicity: O-Glycosylation at the Diffusion Limit

  摘要：

  Nucleophilic substitution reactions of 2-deoxyglycosyl donors indicated that the reactivity of the oxygen nucleophile has a significant impact on stereoselectivity. Employing ethanol as the nucleophile resulted in a 1:1 (alpha:beta) ratio of diastereomers under S(N)1-like reaction conditions. Stercoselective formation of the 2-deoxy-alpha-O-glycoside was only observed when weaker nucleophiles, such as trifluoroethanol, were employed. The lack of stercoselectivity observed in reactions of common oxygen nucleophiles can be attributed to reaction rates of the stereochemistry-determining step that approach the diffusion limit. In this scenario, both faces of the prochiral oxocarbenium ion are subject to nucleophilic addition to afford a statistical mixture of diastercomeric products. Control experiments confirmed that all nucleophilic substitution reactions were performed under kinetic control.

  DOI：

  10.1021/jo902222a

文献信息

• Catalytic ceric ammonium nitrate mediated synthesis of 2-deoxy-1-thioglycosides
  作者：Somak Paul、Narayanaswamy Jayaraman

  DOI：10.1016/j.carres.2004.07.010

  日期：2004.9

  Synthesis of 2-deoxy-1-thioglycosides from glycals, mediated by catalytic amounts of ceric ammonium nitrate is reported. Apart from the 2-deoxy-1-thioglycosides, formation of the 2,3-unsaturated enose, corresponding to the Ferrier product, is also observed, especially for the glucal substrates. A radical oxocarbenium ion and a thiolate intermediates are most likely to mediate the reaction. Upon synthesis

  据报道由催化量的硝酸铈铵介导的由糖类合成2-脱氧-1-硫代糖苷。除了2-脱氧-1-硫代糖苷以外，还观察到形成了对应于Ferrier产物的2,3-不饱和烯键，特别是对于葡萄糖底物。氧羰基自由基离子和硫醇盐中间体最有可能介导该反应。在合成2-脱氧-1-硫代糖苷时，几乎没有与糖基和糖基受体一起进行代表性的糖基化反应，并且仅获得α-异头2-脱氧糖苷。
• Reactions of Various Nucleophiles with <scp>d</scp>-Glucal over Keggin-Type Heteropoly Compounds: A Simple, Rapid, and Expedient Method for the Synthesis of Pseudoglycals
  作者：Ezzat Rafiee、Sara Eavani、Mohammad Joshaghani

  DOI：10.1080/07328300903477796

  日期：2010.1.14

  The reaction of benzyl alcohol with 3,4,6-tri-O-acetyl-d-glucal has been investigated with several heteropoly compounds, and the optimal catalyst is 12-tungstophosphoric acid supported on carbon. In the presence of this catalyst, various alcohols gave the corresponding alkyl and aryl 2,3-unsaturated glycopyranosides in excellent yields and good anomeric selectivity under solvent-free condition. 4,6-Di-O-acetyl-2,3-dideoxy--d-erythro-hex-2-enopyranosyl cyanide and ethyl 4,6-di-O-acetyl-2,3-dideoxy-1-thio--d-erythro-hex-2-enopyranoside have also been prepared with trimethylsilyl cyanide and ethanthiol as nucleophiles, respectively. The catalyst could be easily recovered and reused several times with slight loss of activity. The selectivity to give -anomers predominantly did not show any change in all runs.
• Synthesis of 2-deoxy sugars from glycals
  作者：Subramaniam Sabesan、Susana Neira

  DOI：10.1021/jo00018a054

  日期：1991.8