methyl 2-azido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranoside | 274260-02-5

• 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-azido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranoside
• 英文别名: methyl 2-azido-2-deoxy-4,6-O-benzylidene-β-D-glucopyranoside；(2R,4aR,6R,7R,8R,8aS)-7-azido-6-methoxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-ol
• CAS: 274260-02-5
• 化学式: C₁₄H₁₇N₃O₅
• 分子量: 307.306
• InChiKey: WCSBCLMCXJSBOJ-FAYOZSNISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  71.5
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 2-azido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranoside 在 palladium dihydroxide 、 palladium on activated charcoal 吡啶 、 sodium azide 、 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 氢气 、 sodium methylate 、 溶剂黄146 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 25.0h， 生成 methyl 3-O-(4''-amino-4'',6''-dideoxy-β-D-glucopyranosyl)-4-O-(2',6'-diamino-2',6'-dideoxy-α-D-glucopyranosyl)-2,6-diamino-2,6-dideoxy-β-D-glucopyranoside
  参考文献：
  名称：

  Trisaccharide mimetics of the aminoglycoside antibiotic neomycin

  摘要：

  本研究介绍了一种高度融合的方法，用于化学合成含有 3 至 5 个氨基的 8 种结构相关的三糖。傅立叶变换离子回旋共振质谱（FT-ICR MS）被用来测定三糖与 16S 核糖体 RNA 原型片段结合的解离常数（Kd）。一种在 C-3 位含有 4,6-二脱氧-4-氨基-β-D-吡喃葡萄糖苷分子的化合物显示出低微摩尔范围的结合力。研究发现，糖类结构的微小变化会导致亲和力的巨大差异。所描述的结构-活性关系对开发以 rRNA 为靶标的新型抗生素很有价值。

  DOI：

  10.1039/b517725a
• 作为产物：
  描述：

  methyl 2-amino-2-deoxy-β-D-glucopyranoside 在 triflic azide 、 copper(II) bis(trifluoromethanesulfonate) 、 potassium carbonate 、 copper(II) sulfate 作用下， 以 甲醇 、 水 、 乙腈 为溶剂， 反应 51.0h， 生成 methyl 2-azido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  亲核芳香取代（S N Ar）作为挑战碳水化合物芳基醚的一种方法

  摘要：

  据报道，通过亲核芳族取代（S N Ar）制取碳水化合物-芳基醚的通用方法是可行的。用KHMDS处理后，碳水化合物醇与各种氟化（杂）芳烃之间便会形成C–O键，从而以良好至极佳的收率提供了目标化合物。该方案的显着特征是可商购的芳基化剂，高原子经济性和高区域选择性。芳族醚产物具有广泛用途的潜力，如合成新型手性P，N-配体所举例说明的。

  DOI：

  10.1021/acs.orglett.5b02413

文献信息

• Selectively Deoxyfluorinated <i>N</i> ‐Acetyllactosamine Analogues as ¹⁹ F NMR Probes to Study Carbohydrate‐Galectin Interactions
  作者：Martin Kurfiřt、Martin Dračínský、Lucie Červenková Šťastná、Petra Cuřínová、Vojtěch Hamala、Michaela Hovorková、Pavla Bojarová、Jindřich Karban

  DOI：10.1002/chem.202101752

  日期：2021.9.9

  synthesized a complete series of six mono-deoxyfluorinated analogues of LacNAc, in which each hydroxyl has been selectively replaced by fluorine while the anomeric position has been protected as methyl β-glycoside. Initial evaluation of their binding to human galectin-1 and -3 by ELISA and 19F NMR T2-filter revealed that deoxyfluorination at C3, C4′ and C6′ completely abolished binding to galectin-1 but

  半乳糖凝集素是广泛表达的半乳糖结合凝集素，例如在免疫调节、转移扩散和病原体识别中暗示。N-乙酰乳糖胺（Galβ1-4GlcNAc、LacNAc）及其寡聚或糖基化形式是半乳糖凝集素的天然配体。为了探测半乳糖凝集素的底物特异性和结合模式，我们合成了完整系列的六种 LacNAc 单脱氧氟化类似物，其中每个羟基都被氟选择性取代，而异头位置被保护为甲基β-糖苷。通过 ELISA 和19 F NMR T 2初步评估它们与人半乳糖凝集素-1 和 -3 的结合-filter 显示 C3、C4' 和 C6' 处的脱氧氟化完全消除了与 galectin-1 的结合，但仍可检测到与 galectin-3 的非常弱的结合。此外，C2' 的脱氧氟化导致对 galectin-1 的结合亲和力增加了大约 8 倍，而与 galectin-3 的结合基本上不受影响。亲脂性测量表明，与 GlcNAc 部分的脱氧氟化作用相比，Gal
• Direct Staudinger-Phosphonite Reaction Provides Methylphosphonamidates as Inhibitors of CE4 De-N-acetylases
  作者：Rishikesh Ariyakumaran、Varvara Pokrovskaya、Dustin J. Little、P. Lynne Howell、Mark Nitz

  DOI：10.1002/cbic.201500091

  日期：2015.6.15

  Going through a transition: Methylphosphonamidate‐based transition‐state analogue inhibitors of carbohydrate de‐N‐acetylases were developed by coupling phosphonite and azido sugars. These compounds displayed striking differences in inhibition capabilities against various carbohydrate esterase family 4 (CE4) members, thus key variations within this enzyme class were elucidated.

  经历过渡期：通过偶联亚膦酸酯和叠氮基糖开发了基于碳水化合物的氨基膦酸甲酯的过渡态类似物抑制剂。这些化合物在针对各种碳水化合物酯酶家族4（CE4）成员的抑制能力上显示出惊人的差异，因此阐明了该酶类别内的关键变异。
• Toward synthesis of the regular sequence of heparin: synthesis of two tetrasaccharide precursors
  作者：Ying Zhou、Feng Lin、Jianfang Chen、Biao Yu

  DOI：10.1016/j.carres.2006.02.020

  日期：2006.7

  Two fully protected tetrasaccharides, which represent precursors for the synthesis of the regular sequence of heparin, were synthesized via coupling of a pair of disaccharide trichloroacetimidates with a thioglycoside and a glucosamine derivative, respectively, in a sequential manner. (c) 2006 Elsevier Ltd. All rights reserved.
• α-(2,6)-Sialyltransferase-Catalyzed Sialylations of Conformationally Constrained Oligosaccharides
  作者：M. Carmen Galan、Andre P. Venot、John Glushka、Anne Imberty、Geert-Jan Boons

  DOI：10.1021/ja0169771

  日期：2002.5.1

  It is demonstrated that conformationally restricted oligosaccharides can act as acceptors for glycosyltransferases. Correlation of the conformational properties of N-acetyl lactosamine (Galbeta(1-4)GlcNAc, LacNAc) and several preorganized derivatives with the corresponding apparent kinetic parameters of rat liver alpha-(2,6)-sialyltransferase-catalyzed sialylations revealed that this enzyme recognizes LacNAc in a low energy conformation. Furthermore, small variations in the conformational properties of the acceptors resulted in large differences in catalytic efficiency. Collectively, our data suggest that preorganization of acceptors in conformations that are favorable for recognition by a transferase may improve catalytic efficiencies.
• Synthesis of Two Hyaluronan Trisaccharides
  作者：Bryan K. S. Yeung、Daniel C. Hill、Maria Janicka、Peter A. Petillo

  DOI：10.1021/ol0057075

  日期：2000.5.1

  The synthesis of two hyaluronan trisaccharides, methyl O(beta-D-glucopyranosyluronic acid)-(1,3)-O-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)-(1,4)-O-beta-D-glucopyranosiduronic acid and methyl O-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)-(1,4)-O-beta-D-glycopyranosyluronic acid)-(1,3)-O-(2-acetamido-2-deoxy-beta-D-glucopyranoside are described. Construction of the target molecules was achieved though a combination of the phenyl sulfoxide and trichloroacetimidate glycosylation methodologies. This is the first report on the synthesis of the beta-methyl derivatives, which represent the smallest fragments that incorporate all the structural features of polymeric hyaluronan.