methyl 2,3,6-tri-O-benzyl-4-O-(2,3,4-tri-O-benzyl-6-deoxy-α-D-xylo-hex-5-enopyranosyl)-α-D-glucopyranoside | 244286-71-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,6-tri-O-benzyl-4-O-(2,3,4-tri-O-benzyl-6-deoxy-α-D-xylo-hex-5-enopyranosyl)-α-D-glucopyranoside
• 英文别名: (2S,3R,4S,5S)-2-[(2R,3R,4S,5R,6S)-6-methoxy-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)oxan-3-yl]oxy-6-methylidene-3,4,5-tris(phenylmethoxy)oxane
• CAS: 244286-71-3
• 化学式: C₅₅H₅₈O₁₀
• 分子量: 879.06
• InChiKey: UPUHJCWHRAOUSU-FEMGIJAFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.6
• 重原子数：
  65
• 可旋转键数：
  22
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  92.3
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  methyl 2,3,6-tri-O-benzyl-4-O-(2,3,4-tri-O-benzyl-6-deoxy-α-D-xylo-hex-5-enopyranosyl)-α-D-glucopyranoside 在 三甲基铝 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以75%的产率得到
  参考文献：
  名称：

  含碳水化合物的非糖苷键连接的假二糖和高级假寡糖的合成

  摘要：

  这份简短的综述涵盖了针对含碳水化合物的非糖苷键连接的假二糖或高级假寡糖的合成方法。碳环吡喃糖模拟物（在C-5和C-5a之间饱和或不饱和）通过醚桥，硫醚桥或胺桥连接到碳水化合物或其他Carcarbugars。

  DOI：

  10.1016/j.carres.2009.09.008
• 作为产物：
  描述：

  Phenyl 2,3,6-tri-O-benzyl-4-O-(2,3-di-4,6-O-benzylidene-α-D-glucopyranosyl)-1-thio-β-D-glucopyranoside 在 咪唑 、 N-氯代丁二酰亚胺 、 lithium aluminium tetrahydride 、 三氯化铝 、 碘 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三苯基膦 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 45.0h， 生成 methyl 2,3,6-tri-O-benzyl-4-O-(2,3,4-tri-O-benzyl-6-deoxy-α-D-xylo-hex-5-enopyranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  Pearce, Alan James; Sollogoub, Matthieu; Mallet, Jean-Maurice, European Journal of Organic Chemistry, 1999, # 9, p. 2103 - 2117

  摘要：

  DOI：

文献信息

• Trimethylaluminium promoted rearrangements of unsaturated sugars into cyclohexanes
  作者：Cai Jia、Alan J. Pearce、Yves Blériot、Yongmin Zhang、Li-He Zhang、Matthieu Sollogoub、Pierre Sinaÿ

  DOI：10.1016/j.tetasy.2003.11.029

  日期：2004.2

  Trimethylaluminium induces a stereoselective rearrangement of unsaturated glycosides into polyfunctionalised cyclohexanic rings containing a tertiary alcohol and retaining the anomeric group. In contrast with the previously used triisobutylaluminium, no de-O-benzylation reaction was observed. (C) 2003 Elsevier Ltd. All rights reserved.
• <i>gem</i>-Difluorocarbadisaccharides: Restoring the<i>exo</i>-Anomeric Effect
  作者：Bixue Xu、Luca Unione、Joao Sardinha、Shaoping Wu、Mélanie Ethève-Quelquejeu、Amelia Pilar Rauter、Yves Blériot、Yongmin Zhang、Sonsoles Martín-Santamaría、Dolores Díaz、Jesus Jiménez-Barbero、Matthieu Sollogoub

  DOI：10.1002/anie.201405008

  日期：2014.9.1

  AbstractMolecular mimicry is an essential part of the development of drugs and molecular probes. In the chemical glycobiology field, although many glycomimetics have been developed in the past years, it has been considered that many failures in their use are related to the lack of the anomeric effects in these analogues. Additionally, the origin of the anomeric effects is still the subject of virulent scientific debates. Herein, by combining chemical synthesis, NMR methods, and theoretical calculations, we show that it is possible to restore the anomeric effect for an acetal when replacing one of the oxygen atoms by a CF2 group. This result provides key findings in chemical sciences. On the one hand, it strongly suggests the key relevance of the stereoelectronic component of the anomeric effect. On the other hand, the CF2 analogue adopts the natural glycoside conformation, which might provide new avenues for sugar‐based drug design.