methyl 3,4,6-tri-O-benzyl-β-D-arabinohexopyranoside-2-ulose | 40246-31-9

• 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: methyl 3,4,6-tri-O-benzyl-β-D-arabinohexopyranoside-2-ulose
• 英文别名: Methyl-3,4,6-tri-O-benzyl-β-D-arabino-hexosidulose；methyl 3,4,6-tri-O-benzyl-beta-d-arabino-hexopyranosid-2-ulose；(2R,4S,5R,6R)-2-methoxy-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-one
• CAS: 40246-31-9
• 化学式: C₂₈H₃₀O₆
• 分子量: 462.543
• InChiKey: MUCQZWTZPSXQMQ-YULOIDQLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  34
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 3,4,6-tri-O-benzyl-β-D-arabinohexopyranoside-2-ulose 在 potassium carbonate 作用下， 以 水 、 甲苯 为溶剂， 反应 20.0h， 以85%的产率得到methyl 3,6-Di-O-benzyl-4-deoxy-β-D-glycero-hex-3-enopyranoside-2-ulose
  参考文献：
  名称：

  Carbohydrate-Derived 3,2-Enolones in the Base-Catalyzed Rearrangement to Highly Functionalized C 4-Quaternary 4-Hydroxy-2-cyclopentenones

  摘要：

  3,4,6‐O‐benzylated β‐2‐ulosides were subjected to 3,4‐elimination, providing carbohydrate‐derived 3,2‐enolones. Reaction of these enolones under basic conditions in polar aprotic solvents afforded highly functionalized racemic 5‐alkoxy‐2‐benzyloxy‐4‐benzyloxymethyl‐4‐hydroxy‐2‐cyclopentenones. The influence of the nature of the base as well as solvent effects were investigated. The rearrangement products obtained from this reaction exhibit a 4‐hydroxy‐C4‐quaternary stereogenic center. In contrast, the rearrangement of comparable dihydropyran‐3‐ones was reported to furnish the C5‐quaternary 5‐hydroxy‐2‐cyclopentenones. Plausible mechanisms for the described rearrangement and subsequent isomerization processes are given.

  DOI：

  10.1002/ejoc.201700846
• 作为产物：
  描述：

  methyl 3,4,6-tri-O-benzyl-β-D-glucopyranoside 在 乙酸酐 作用下， 以 二甲基亚砜 为溶剂， 生成 methyl 3,4,6-tri-O-benzyl-β-D-arabinohexopyranoside-2-ulose
  参考文献：
  名称：

  Experimental evidence on the hydroxymethyl group conformation in alkyl β-d-mannopyranosides

  摘要：

  A rotational population Study of the hydroxymethyl group of alkyl beta-D-mannopyranosides was performed by means of CD and NMR spectroscopy. Three different benzyl, acetyl, and p-bromobenzoyl series of alkyl beta-D-mannopyranosides with different chiral and nonchiral aglycons were synthesized and analyzed. Different rotational populations were observed for each series by changing the structure of the aglycon. The results showed a clear correlation between the rotational population of the hydroxymethyl group around the C5-C6 bond and the pK(a) of the bonded alcohol (aglycon). The population of the gt rotamer gradually increased as the pK(a) increased while that of the gg rotamer decreased and the population of the tg rotamer remained almost constant. This is explained by the exo-anomeric effect. For chiral alkyl derivatives, the results also showed a close dependence on the absolute configuration of the aglycon. Comparison of rotational population anomers revealed the dependence or the hydroxymethyl group on the anomeric configuration and a greater dependence on the aglycon structure in the beta anomers. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.06.019