ethyl 2-deoxy-3,4,6-tri-O-acetyl-1-thio-α-D-arabinohexopyranoside | 135824-52-1

• 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-α-D-arabinohexopyranoside
• 英文别名: ethyl 3,4,6-tri-O-acetyl-2-deoxy-1-thio-α-D-arabinohexopyranoside；ethyl 2-deoxy-3,4,6-tri-O-acetyl-1-thio-α-D-hexopyranoside；[(2R,3S,4R,6R)-3,4-diacetyloxy-6-ethylsulfanyloxan-2-yl]methyl acetate
• CAS: 135824-52-1
• 化学式: C₁₄H₂₂O₇S
• 分子量: 334.39
• InChiKey: FTPWDDWCHUEJQV-SYQHCUMBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.28
• 重原子数：
  22.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  88.13
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 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

• Systematic study on free radical hydrothiolation of unsaturated monosaccharide derivatives with exo- and endocyclic double bonds
  作者：László Lázár、Magdolna Csávás、Ádám Hadházi、Mihály Herczeg、Marietta Tóth、László Somsák、Terézia Barna、Pál Herczegh、Anikó Borbás

  DOI：10.1039/c3ob40547h

  日期：——

  reacted with various thiols by irradiation with UV light in the presence of a cleavable photoinitiator. The photoinduced radical-mediated hydrothiolation reactions showed highly varying overall conversions depending not only on the substitution pattern and electron-density of the double bond but also on the nature and substitution pattern of the thiol partner. Out of the applied thiols thiophenol, producing

  通过在可裂解的光引发剂的存在下用紫外线照射，使糖的外环和内环双键以及烯键的末端双键与各种硫醇反应。光诱导的自由基介导的氢硫醇化反应显示出很大变化的总转化率，这不仅取决于双键的取代方式和电子密度，还取决于硫醇配偶体的性质和取代方式。在所施加的硫醇中，产生高度稳定的噻吩基的硫酚对每种烯烃的反应性最低。在大多数情况下，氢硫醇化反应具有完全的区域选择性和立体选择性。将1,2：3,4-二-O-异亚丙基-6-硫代-α- D-吡喃半乳糖成功添加到2,3-不饱和N-乙酰神经氨酸衍生物提供（3→6）-S连接的假二糖，表明带有吸电子取代基的Neu5Ac-2-ene的内环双键在光诱导的硫醇-烯偶联反应中显示出足够的反应性。 。
• 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