(1,2-Di-O-hexadecyl-sn-3-glyceryl)-O-(2,6-di-O-benzoyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzoyl-β-D-glucopyranoside | 332075-25-9

• 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: (1,2-Di-O-hexadecyl-sn-3-glyceryl)-O-(2,6-di-O-benzoyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzoyl-β-D-glucopyranoside
• CAS: 332075-25-9
• 化学式: C₈₂H₁₁₂O₁₈
• 分子量: 1385.78
• InChiKey: LBJYZGDRJLVSHG-FOFWFSFQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.31
• 重原子数：
  100.0
• 可旋转键数：
  50.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  227.34
• 氢给体数：
  2.0
• 氢受体数：
  18.0

反应信息

• 作为反应物：
  描述：

  (1,2-Di-O-hexadecyl-sn-3-glyceryl)-O-(2,6-di-O-benzoyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzoyl-β-D-glucopyranoside 在 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 以97%的产率得到(1,2-Di-O-hexadecenyl-sn-3-glyceryl)-O-(β-D-galactopyranosyl)(1->4-β-D-glucopyranoside
  参考文献：
  名称：

  Thermodynamic Properties and Swelling Behavior of Glycolipid Monolayers at Interfaces

  摘要：

  Synthetic glycolipids with lactose headgroups (N = 1, 2, and 3) were synthesized, and their thermodynamic properties were systematically studied by Langmuir isotherms using a film balance. The molar transition entropy and the molar latent heat were calculated by applying the Clausius-Clapeyron equation. It has been demonstrated that the phase behavior of the glycolipid monolayers is comparable to that of ordinary phospholipids, despite the lower degree of cooperativity between the larger headgroups. The glycolipid monolayer was transferred onto a solid surface by Langmuir-Blodgett deposition, and the swelling behavior was investigated by ellipsometry. The surface grafting density was precisely controlled, and the water disjoining pressure inside the lactose layer was quantitatively measured. The measured swelling curves were analyzed in terms of the theoretical descriptions for the grafted polymer "brushes". For the lipids with lactose units of N = 2 and 3, the disjoining pressure-thickness relation could fit very well to these theoretical approaches, even though the statistical limit N much greater than 1 is hardly fulfilled. The results suggest entropic effects of the headgroups on the interaction between the neighboring molecules. On the other hand, the theoretical description of the swelling behavior of the lipids with one lactose unit failed due to the "rodlike" structure of lactose. The unique properties of these glycolipids at interfaces, such as (i) the phase behavior comparable to that of ordinary phospholipids and (ii) the "polymer-like" swelling behavior, play very important roles in biological systems. Mimicking the complex interactions between oligosaccharide headgroups in the plasma membranes, the synthetic glycolipids designed in this study are quite realistic models for the glycocalix.

  DOI：

  10.1021/jp0028103
• 作为产物：
  描述：

  (1,2-Di-O-hexadecyl-sn-3-glyceryl)-O-(2,6-di-O-benzoyl-3,4-di-O-isopropylidene-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzoyl-β-D-glucopyranoside 在 三氟乙酸 作用下， 反应 6.0h， 以98%的产率得到(1,2-Di-O-hexadecyl-sn-3-glyceryl)-O-(2,6-di-O-benzoyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzoyl-β-D-glucopyranoside
  参考文献：
  名称：

  Thermodynamic Properties and Swelling Behavior of Glycolipid Monolayers at Interfaces

  摘要：

  Synthetic glycolipids with lactose headgroups (N = 1, 2, and 3) were synthesized, and their thermodynamic properties were systematically studied by Langmuir isotherms using a film balance. The molar transition entropy and the molar latent heat were calculated by applying the Clausius-Clapeyron equation. It has been demonstrated that the phase behavior of the glycolipid monolayers is comparable to that of ordinary phospholipids, despite the lower degree of cooperativity between the larger headgroups. The glycolipid monolayer was transferred onto a solid surface by Langmuir-Blodgett deposition, and the swelling behavior was investigated by ellipsometry. The surface grafting density was precisely controlled, and the water disjoining pressure inside the lactose layer was quantitatively measured. The measured swelling curves were analyzed in terms of the theoretical descriptions for the grafted polymer "brushes". For the lipids with lactose units of N = 2 and 3, the disjoining pressure-thickness relation could fit very well to these theoretical approaches, even though the statistical limit N much greater than 1 is hardly fulfilled. The results suggest entropic effects of the headgroups on the interaction between the neighboring molecules. On the other hand, the theoretical description of the swelling behavior of the lipids with one lactose unit failed due to the "rodlike" structure of lactose. The unique properties of these glycolipids at interfaces, such as (i) the phase behavior comparable to that of ordinary phospholipids and (ii) the "polymer-like" swelling behavior, play very important roles in biological systems. Mimicking the complex interactions between oligosaccharide headgroups in the plasma membranes, the synthetic glycolipids designed in this study are quite realistic models for the glycocalix.

  DOI：

  10.1021/jp0028103

文献信息

• Synthesis and Molecular Tumbling Properties of Sialyl Lewis X and Derived Neoglycolipids
  作者：Christian Gege、Armin Geyer、Richard R. Schmidt

  DOI：10.1002/1521-3765(20020603)8:11<2454::aid-chem2454>3.0.co;2-u

  日期：2002.6.3

  applied to the synthesis of the corresponding Lewis X (LeX) derivatives. The glycolipids were inserted in model membranes, and the tumbling frequencies of the sLex tetrasaccharide epitopes were then analysed by NMR spectroscopy. A nonaethylene glycol spacer decouples the carbohydrate moiety from the membrane mobility while (oligo-)lactoses act as more rigid distance keepers between the Lewis epitope and

  唾液酸化的路易斯X（sLeX）表位已成为生物学研究的主要目标，因为它通过与选择素结合而在炎症中发挥作用。该表位位于糖鞘脂的末端，并且乳糖单元充当神经酰胺部分的间隔基。本文着重于间隔物结构和间隔物长度对sLeX表位迁移率的影响。为此目的，合成了具有一个，两个或三个乳糖单元作为sLeX四糖表位和膜锚之间间隔物的sLex新糖脂1a-c。该合成策略也被应用于相应的Lewis X（LeX）衍生物的合成。将糖脂插入模型膜中，然后通过NMR光谱分析sLex四糖表位的翻转频率。九甘醇间隔基使碳水化合物部分与膜的迁移性脱钩，而（低聚）乳糖酶则充当路易斯表位与膜表面之间更牢固的距离保持物。通过分析旋转相关时间可以量化不同程度的解耦。
• Regioselective Acylation of Diols and Triols: The Cyanide Effect
  作者：Peng Peng、Michael Linseis、Rainer F. Winter、Richard R. Schmidt

  DOI：10.1021/jacs.6b02454

  日期：2016.5.11

  positioned hydroxy groups. As cyanide is capable of various kinds of hydrogen bonding and as it is a quite strong sterically nondemanding base, regioselective O-acylations should be possible at low temperatures even at sterically congested positions, thus permitting formation and also isolation of the kinetic product. Indeed, 1,2-cis-diols, having an equatorial and an axial hydroxy group, benzoyl cyanide

  碳水化合物化学的中心主题包括碳水化合物的结构修饰和寡糖合成。两者都需要受区域选择性保护的构建块，这些构建块主要通过间接多步程序获得。因此，需要针对特定​​羟基的直接保护方法。双氢键最终将区分不同位置的羟基。由于氰化物能够形成各种氢键，并且它是一种非常强的空间要求不高的碱，因此即使在空间拥挤的位置，也应该可以在低温下进行区域选择性 O-酰化，从而允许形成和分离动力学产物。实际上，具有赤道和轴羟基的 1,2-顺式二醇、苯甲酰氰或乙酰氰作为酰化剂，和 DMAP 作为催化剂在 -78°C 下产率热力学上不利的轴向 O-酰化产物；在这些条件下未观察到酰基迁移。这种现象被 3,4-O-未保护的半乳糖和吡喃岩藻糖苷以及 2,3-O-未保护的吡喃甘露糖苷证实。即使对于作为三醇的 3,4,6-O-未保护的吡喃半乳糖苷，轴向 4-O-酰化也明显快于伯 6-羟基的 O-酰化。氢键对这种不寻常的区域选择性的重要性可以通过