methyl 2-O-benzyl-4,6-O-(p-methoxybenzylidene)-α-D-glucopyranoside | 162583-81-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 2-O-benzyl-4,6-O-(p-methoxybenzylidene)-α-D-glucopyranoside
• 英文别名: (+)-methyl 2-O-benzyl-4,6-O-anisylidene-α-D-glucopyranoside；Gcnyngrghgoidd-lyszkaazsa-；(2R,4aR,6S,7R,8S,8aS)-6-methoxy-2-(4-methoxyphenyl)-7-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-ol
• CAS: 162583-81-5
• 化学式: C₂₂H₂₆O₇
• 分子量: 402.444
• InChiKey: GCNYNGRGHGOIDD-LYSZKAAZSA-N

物化性质

• 熔点：
  136-138 °C(Solvent: Ethyl acetate)
• 沸点：
  570.2±50.0 °C(predicted)
• 密度：
  1.28±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  75.6
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 2-O-benzyl-4,6-O-(p-methoxybenzylidene)-α-D-glucopyranoside 在 盐酸 、 lithium aluminium tetrahydride 、 三氯化铝 、 (环戊二烯基)2ZR 、 草酰氯 、 三氟化硼乙醚 、 potassium tert-butylate 、 sodium hydride 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 生成 (1R,2S,3S,4R,5R)-3-(benzyloxy)-1,2,4-trihydroxy-5-vinylcyclopentane
  参考文献：
  名称：

  Pentagon IP3: Synthesis of a Ring-Contracted Mimic of a Second Messenger

  摘要：

  DOI：

  10.1021/ja00116a046
• 作为产物：
  描述：

  4-甲氧基苯甲醛二甲缩醛 在 4 A molecular sieve 、 四丁基碘化铵 、 二正丁基氧化锡 、 对甲苯磺酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 18.0h， 生成 methyl 2-O-benzyl-4,6-O-(p-methoxybenzylidene)-α-D-glucopyranoside
  参考文献：
  名称：

  Pentagon IP3: Synthesis of a Ring-Contracted Mimic of a Second Messenger

  摘要：

  DOI：

  10.1021/ja00116a046

文献信息

• Chemical mapping of the active site of the glucoamylase of<i>Aspergillus niger</i>
  作者：Raymond U. Lemieux、Ulrike Spohr、Mimi Bach、Dale R. Cameron、Monica M. Palcic、Torben P. Frandsen、Bjarne B. Stoffer、Birte Svensson

  DOI：10.1139/v96-036

  日期：1996.3.1

  A recently developed technique for the probing of the combining sites of lectins and antibodies, to establish the structure of the epitope that is involved in the binding of an oligosaccharide, is used to study the binding of methyl α-isomaltoside by the enzyme glucoamylase. The procedure involved the determination of the effects on the kinetics of hydrolysis of both monodeoxygenation and mono-O-methylation at each of the seven hydroxyl groups in order to gain an estimate of the differential changes in the free energies of activation, ΔΔG^≠. As expected, from previous publications, both deoxygenation and O-methylation of OH-4 (reducing unit), OH-4′, or OH-6′ strongly hindered hydrolysis, whereas the kinetics were virtually unaffected by either the substitutions at OH-2 or structural changes at C-1. The substitutions at OH-3 caused increases of 2.1 and 1.9 kcal/mol in the ΔΔG^≠. In contrast, whereas deoxygenation of either OH-2′ or OH-3′ caused much smaller (0.96 and 0.52 kcal/mol) increases in ΔΔG^≠, the mono-O-methylations resulted in severe steric hindrance to the formation of the activated complex. The relatively weak effects of deoxygenation suggest that the hydroxyl groups are replaced by water molecules and thereby participate in the binding by contributing effective complementarity. Methyl α-isomaltoside was docked into the combining site of the X-ray crystal structure at 2.4 Å resolution of the complex with the inhibitor acarbose. A fit free of steric interactions with the protein was found that has the methyl α-glucopyranoside unit in the normal⁴C₁conformation and the other glucose unit approaching a half-chair conformation with the interunit fragment defined by the torsion angles [Formula: see text] The model provides a network of hydrogen bonds that appears to well represent the activated complex formed by the glucoamylase with both maltose and isomaltose since the structures appear to provide a sound rationale for both the specificity and catalysis provided by the enzyme. Key words: monodeoxy and mono-O-methyl derivatives of methyl α-isomaltoside, enzyme binding domain, functioning of glucoamylase, differential changes in free energy of activation, characteristics of hydrogen bonding networks.

  最近开发的一种技术用于探测凝集素和抗体的结合位点，以建立与寡糖结合中涉及的表位的结构，用于研究酶葡萄糖酶对甲基α-异麦芽糖的结合。该过程涉及确定对水解动力学的影响，包括每个七个羟基的单去氧和单-O-甲基化，以获得活化自由能的差异变化ΔΔG^≠的估计。如预期的那样，根据先前的发表，OH-4（还原单元）、OH-4'或OH-6'的脱氧和O-甲基化强烈阻碍了水解，而OH-2的置换或C-1的结构变化几乎不影响动力学。OH-3的置换导致ΔΔG^≠增加了2.1和1.9 kcal/mol。相比之下，OH-2'或OH-3'的脱氧导致ΔΔG^≠增加较小（0.96和0.52 kcal/mol），而单-O-甲基化导致了对激活复合物形成的严重位阻。脱氧的相对较弱影响表明，羟基被水分子取代，从而通过提供有效的互补性参与结合。甲基α-异麦芽糖被对接到X射线晶体结构的结合位点，分辨率为2.4 Å的复合物与抑制剂阿卡波糖。找到了与蛋白质无位阻相互作用的适合，其中甲基α-葡萄糖吡喃糖单元处于正常的4C1构象，另一个葡萄糖单元接近半椅构象，其间单元片段由扭转角度定义[Formula: see text]该模型提供了一个氢键网络，似乎很好地代表了由葡萄糖酶与麦芽糖和异麦芽糖形成的激活复合物，因为这些结构似乎为酶提供的特异性和催化提供了合理的基础。关键词：甲基α-异麦芽糖的单去氧和单-O-甲基衍生物，酶结合结构域，葡萄糖酶的功能，活化自由能的差异变化，氢键网络的特性。
• A type 2 Ferrier rearrangement-based synthesis of d-myo-inositol 1,4,5-trisphosphate
  作者：Neil S. Keddie、Geert Bultynck、Tomas Luyten、Alexandra M.Z. Slawin、Stuart J. Conway

  DOI：10.1016/j.tetasy.2009.03.006

  日期：2009.5

  The synthesis of D-myo-inositol 1,4,5-trisphosphate (InsP(3)) from methyl alpha-D-glucopyranose, via a type 2 Ferrier rearrangement is reported. A key intermediate in this synthesis possesses orthogonal protecting groups at the 1-, 4- and 5-position, making it a versatile starting point for the synthesis of unnatural InsP(3) derivatives. Biological evaluation of the synthetic InsP(3) demonstrates that this compound evokes selective Ca2+ release via activation of InsP(3) receptors. (C) 2009 Elsevier Ltd. All rights reserved.
• Pentagon IP3: Synthesis of a Ring-Contracted Mimic of a Second Messenger
  作者：Andrew M. Riley、David J. Jenkins、Barry V. L. Potter

  DOI：10.1021/ja00116a046

  日期：1995.3