Methyl 2,3-di-O-benzyl-4-O-methyl-α-D-glucopyranoside | 51433-17-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 2,3-di-O-benzyl-4-O-methyl-α-D-glucopyranoside
• CAS: 51433-17-1
• 化学式: C₂₂H₂₈O₆
• 分子量: 388.461
• InChiKey: HCYCZKLJCIINFR-BDHVOXNPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.54
• 重原子数：
  28.0
• 可旋转键数：
  9.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  66.38
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  Methyl 2,3-di-O-benzyl-4-O-methyl-α-D-glucopyranoside 在 碳酸氢钠 、 potassium bromide 2,2,6,6-tetramethyl-piperidine-N-oxyl 、 sodium hypochlorite 、 四丁基溴化铵 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以80%的产率得到Methyl 2,3-di-O-benzyl-4-O-methyl-α-D-glucopyranosiduronic acid
  参考文献：
  名称：

  Synthesis and Acid-Catalyzed Hydrolysis of Some 3-(4-Methoxyphenyl)propyl Glucuronates

  摘要：

  3-(4-甲氧基苯基)丙基D-葡萄糖醛酸酯、3-(4-甲氧基苯基)丙基甲基4-O-甲基-α-D葡萄糖醛酸酯、3-(4-甲氧基苯基)丙基1,2,3,4-四-O-乙酰基-α-D葡萄糖醛酸酯和3-(4-甲氧基苯基)丙基1,2-(S):3,5-二-O-苯甲醛基-α-D葡萄糖呋喃醛酸酯被制备为酯木质素-糖类键的模型物质。在20℃下，用LC-DAD分析测量了在乙腈-水3:1的1 M HCl中制备的化合物的酸催化水解速率，并表明酯键对酸水解的稳定性较低。

  DOI：

  10.1135/cccc20001609
• 作为产物：
  描述：

  methyl 2,3-di-O-benzyl-6-O-tosyl-α-D-glucopyranoside 在 sodium hydroxide 、 tertiary amine 、 亚氨基二乙酸 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 生成 Methyl 2,3-di-O-benzyl-4-O-methyl-α-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of novel amino acid glycoside conjugates

  摘要：

  A new class of non-anomeric amino acid glycoconjugates can be prepared starting from either omega-amino- or omega-halodeoxyglucosides. Treatment of an ether-protected methyl 7-amino-6,7-dideoxy-alpha-D-glucoheptopyranoside with methyl aspartate isocyanate gave an urea-linked conjugate of methyl glucoheptopyranoside and aspartic acid. Nucleophilic displacement of the ether-protected methyl 6-chloro-6-deoxy-alpha-D-glucopyranoside with potassium succinimide followed by imide ring opening and amidation of the succinic acid monoamide with dimethyl iminodiacetate led to a conjugate of methyl 6-amino-6-deoxy-alpha-D-glucopyranoside and iminodiacetate bridged by succinate. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0008-6215(97)00091-8

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。
• Synthesis of <scp>l</scp>-Pyranosides by Hydroboration of Hex-5-enopyranosides Revisited
  作者：Grzegorz Łopatkiewicz、Jacek Mlynarski

  DOI：10.1021/acs.joc.6b01243

  日期：2016.9.2

  Extensive study of the diastereoselective synthesis of l-pyranosides utilizing hydroboration of substituted exo-glucals (5-enopyranosides) obtained from d-sugars is presented. On the basis of this study we present the empirical rules describing the reaction stereoselectivity and the correlation between the yield of the l-ido product and the size of protecting groups used. Application of these guidelines

  提出了广泛的研究，利用从d-糖获得的取代的exo-葡糖醛酸（5- enopyranosides）的硼氢化方法对l- pyranosides进行非对映选择性合成。在这项研究的基础上，我们给出了描述反应立体选择性的经验法则，以及l - IDO产物的收率和所用保护基团大小之间的相关性。这些准则的应用表明，甲基2,3-的硼氢化ø甲基-6-脱氧α- d -木糖-己-5-烯吡喃糖苷导致的独家形成升- IDO产品产量高。该方法可以成功地用于合成作为抗凝血药必不可少的非对映体选择性优于以前发表的协议的1-异丁烯二酸。
• Synthesis of Non‐anomeric Spiro‐Fused Bicyclic Sugar Derivatives by Light‐Mediated 1,5‐Hydrogen Atom Transfer (HAT) Process
  作者：Anjali Aghi、Akanksha Singh Baghel、Amit Kumar

  DOI：10.1002/ejoc.202200847

  日期：2022.11.7

  and efficient synthesis for the construction of the complex non-anomeric spiro-fused bicyclic sugar derivatives from glycosyl 6-trichloroacetimidates under visible light conditions was developed. The overall reaction proceeds via in situ generation of imidate nitrogen-centered radicals followed by 1,5-hydrogen atom transfer to form the intramolecular carbon-nitrogen (C−N) bond.

  开发了一种温和有效的合成方法，用于在可见光条件下从糖基 6-三氯乙酰亚胺酯构建复杂的非异头螺稠合双环糖衍生物。整个反应通过原位生成以亚氨基氮为中心的自由基进行，然后通过 1,5-氢原子转移形成分子内碳-氮 (C-N) 键。