(2,6-Di-O-benzoyl-3,4-di-O-isopropylidene-ν-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzoyl-β-D-glucopyranosyl trichloroacetimidate

• 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: (2,6-Di-O-benzoyl-3,4-di-O-isopropylidene-ν-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzoyl-β-D-glucopyranosyl trichloroacetimidate
• 英文别名: (2,6-di-O-benzoyl-3,4-O-isopropylidene-β-D-galactopyranosyl)-(1→4)-(2,3,6-tri-O-benzoyl-α-D-glucopyranosyl)trichloroacetimidate；O-(4-O-(2,6-di-O-benzoyl-3,4-O-isopropylidene-β-D-galactopyranosyl)-2,3,6-tri-O-benzoyl-α-D-glucopyranosyl) trichloroacetimidate；2,3,6,2',6'-penta-O-benzoyl-3',4'-O-isopropylidene-1-O-α-lactosyl trichloroacetimidate；2,3,6,2',6'-penta-O-benzoyl-3',4'-O-isopropylidene-α-lactosyl trichloroacetimidate；3',4'-O-isopropylidene-2,3,6,2',6'-penta-O-benzoyl-1-O-α-lactosyl trichloroacetimidate；3',4'-O-isopropylidene-2,3,6,2',6'-penta-O-benzoyl-α-lactosyl trichloroacetimidate；[(3aS,4R,6S,7R,7aS)-7-benzoyloxy-6-[(2R,3R,4S,5R,6R)-4,5-dibenzoyloxy-2-(benzoyloxymethyl)-6-(2,2,2-trichloroethanimidoyl)oxyoxan-3-yl]oxy-2,2-dimethyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl]methyl benzoate
• 化学式: C₅₂H₄₆Cl₃NO₁₆
• 分子量: 1047.29
• InChiKey: VZTIXNGLHBKIED-CMSYHTEASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10
• 重原子数：
  72
• 可旋转键数：
  21
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  211
• 氢给体数：
  1
• 氢受体数：
  17

反应信息

• 作为反应物：
  描述：

  1,2-o-二十六基-sn-甘油 、 (2,6-Di-O-benzoyl-3,4-di-O-isopropylidene-ν-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzoyl-β-D-glucopyranosyl trichloroacetimidate 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以94%的产率得到(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
  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：

  Lactose 在 4-二甲氨基吡啶 、 N-溴代丁二酰亚胺(NBS) 、 sodium methylate 、 sodium acetate 、 四氯化锡 、 对甲苯磺酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 吡啶 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 206.83h， 生成 (2,6-Di-O-benzoyl-3,4-di-O-isopropylidene-ν-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzoyl-β-D-glucopyranosyl trichloroacetimidate
  参考文献：
  名称：

  A divergent approach to the synthesis of iGb3 sugar and lipid analogues via a lactosyl 2-azido-sphingosine intermediate

  摘要：

  异地三糖脂鞘氨醇（iGb3，1）是一种免疫调节糖脂，它结合到CD1d并呈现给不变天然杀伤T细胞受体（iNKT细胞）的T细胞受体（TCR）。

  DOI：

  10.1039/c4ob00241e

文献信息

• Synthesis of oligosaccharide fragments of the Streptococcus pneumoniae type 14 capsular polysaccharide and their neoglycoconjugates with bovine serum albumin
  作者：E. V. Sukhova、D. V. Yashunsky、Yu. E. Tsvetkov、E. A. Kurbatova、N. E. Nifantiev

  DOI：10.1007/s11172-014-0462-5

  日期：2014.2

  2-Aminoethyl glycosides of tetra-, hexa- and octasaccharide fragments of the bacteria Streptococcus pneumoniae type 14 capsular polysaccharide were synthesized within a project directed to the development of pneumococcal conjugated vaccine based on synthetic carbohydrate ligands. Squarate method was used to obtain neoglycoconjugates of the synthesized oligosaccharides with bovine serum albumin.

  合成了肺炎链球菌14型荚膜多糖的四糖、六糖和八糖片段的2-氨乙基糖苷，这项工作是为了开发基于合成碳水化合物配体的肺炎球菌结合疫苗。采用方形酸法获得了合成的寡糖与牛血清白蛋白的新糖结合物。
• Facile Synthesis of Tumor-Associated Carbohydrate Antigen Ganglioside GM₃from Sialic Acid, Lactose, and Serine
  作者：Guo-wen Xing、Li Chen、Fen-fen Liang

  DOI：10.1002/ejoc.200900778

  日期：2009.12

  Ganglioside GM3 [α-Neu5Ac-(2,3)-β-Gal-(1,4)-β-Glc-(1,1)-Cer; 1] is considered as an important tumor-associated carbohydrate antigen, which can be used in the development of tumor vaccine. In this study, a facile and convergent synthetic strategy for GM3 was developed, and the preparation of three building blocks started from the most readily available compounds sialic acid, lactose, and L-serine. Ceramide

  神经节苷脂 GM3 [α-Neu5Ac-(2,3)-β-Gal-(1,4)-β-Glc-(1,1)-Cer; 1] 被认为是一种重要的肿瘤相关糖类抗原，可用于肿瘤疫苗的开发。在这项研究中，开发了一种简便且收敛的 GM3 合成策略，并从最容易获得的化合物唾液酸、乳糖和 L-丝氨酸开始制备三个构建块。神经酰胺苷元 9 由 L-丝氨酸分 13 步构建，总产率为 6%，而乳糖基三氯乙酰亚胺酯 14 由乳糖分 7 步合成，产率为 25%。以我组开发的新型N-乙酰-5-N,4-O-恶唑烷酮保护的对甲苯硫代唾液酸15为供体，苯甲酰基保护的乳糖神经酰胺二醇23的唾液酸化反应以54%的收率成功完成。我们的策略在五个步骤中提供了更短的 GM3 线性全合成，总产率为 26%。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• A divergent approach to the synthesis of iGb3 sugar and lipid analogues via a lactosyl 2-azido-sphingosine intermediate
  作者：Janice M. H. Cheng、Emma M. Dangerfield、Mattie S. M. Timmer、Bridget L. Stocker

  DOI：10.1039/c4ob00241e

  日期：——

  Isoglobotrihexosylceramide (iGb3, 1) is an immunomodulatory glycolipid that binds to CD1d and is presented to the T-cell receptor (TCR) of invariant natural killer T (iNKT) cells.

  异地三糖脂鞘氨醇（iGb3，1）是一种免疫调节糖脂，它结合到CD1d并呈现给不变天然杀伤T细胞受体（iNKT细胞）的T细胞受体（TCR）。
• Thermodynamic Properties and Swelling Behavior of Glycolipid Monolayers at Interfaces
  作者：Matthias F. Schneider、Gerald Mathe、Motomu Tanaka、Christian Gege and、Richard R. Schmidt

  DOI：10.1021/jp0028103

  日期：2001.6.1

  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.