methyl (allyl 2,3,4-tri-O-acetyl-β-D-glucopyranosid)uronate | 114663-53-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (allyl 2,3,4-tri-O-acetyl-β-D-glucopyranosid)uronate
• 英文别名: methyl (2S,3S,4S,5R,6R)-3,4,5-triacetyloxy-6-prop-2-enoxyoxane-2-carboxylate
• CAS: 114663-53-5
• 化学式: C₁₆H₂₂O₁₀
• 分子量: 374.345
• InChiKey: ZMKKPVNDESHQBT-GRYWWWGRSA-N

物化性质

• 熔点：
  134-135 °C(Solv: ethyl acetate (141-78-6); heptane (142-82-5))
• 沸点：
  416.3±45.0 °C(Predicted)
• 密度：
  1.26±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  26
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  124
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  methyl (allyl 2,3,4-tri-O-acetyl-β-D-glucopyranosid)uronate 在 吡啶 、 盐酸 、 sodium acetate 、 溶剂黄146 、 六甲基二硅氮烷 、 potassium iodide 、 palladium dichloride 、 silver(l) oxide 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 31.5h， 生成 methyl 2,3,4-tri-O-benzyl-β-D-glucopyranuronate
  参考文献：
  名称：

  Comparison of Several Glucuronate Glycosyl Donors

  摘要：

  Methyl 3,4-di-O-benzyl-[(S)-1,2-O-(1-cyanoethylidene)]-alpha-D-glucopyranuronate (12), methyl 3,4-di-O-benzyl-[(S)-1,2-O-(1-ethoxyethylidene)]-alpha-D-glucopyranuronate (14), methyl 2-O-acetyl-3,4-di-O-benzyl-alpha-D-glucopyranuronate bromide (15), methyl (2-O-acetyl-3,4-di-O-benzyl-alpha-D-glucopyranosyl)uronate trichloroacetimidate (17), and methyl (2,3,4-tri-O-benzyl-alpha/beta-D-glucopyranosyl)uronate trichloroacetimidate (30) were synthesized and used as glycosyl donors. Glycosylation reactions of 12 with (5-R)-2,3,4,5-tetrahydro-5-trityloxymethyl-2-furanone (32) and 14,15,17 with the corresponding (5-R)-2,3,4,5-tetrahydro-5-hydroxymethyl-2-furanone (31) provided the exclusively beta-linked glucuronide 33 in 69%, 28%, 45%, and 71% yield, respectively. The coupling of donor 30 with acceptor 31 furnished the glucuronated lactone 35 in 70% yield with a surprisingly high content (20%) of the undesired alpha-linked sugar residue. The structure of 33 was proved by NMR and X-ray diffraction studies. In a model reaction a complete deprotection procedure of the glucuronic acid lactone conjugation was demonstrated.

  DOI：

  10.1081/car-120026603
• 作为产物：
  描述：

  allyl 2,3,4-tri-O-acetyl-6-O-trityl-β-D-glucopyranoside 在 chromium(VI) oxide 、 硫酸 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 0.83h， 生成 methyl (allyl 2,3,4-tri-O-acetyl-β-D-glucopyranosid)uronate
  参考文献：
  名称：

  Introduction of monosaccharides having functional groups onto a carbosilane dendrimer: A broadly applicable one-pot reaction in liquid ammonia involving Birch reduction and subsequent Sn2 reaction

  摘要：

  Benzylthioalkyl glycosides of D-glucuronic acid, N-acetyl-D-glucosamine, and N-acetylneuraminic acid (common monosaccharide constituents of natural oligosaccharide chains) have been prepared as sulfide precursors for the carbohydrate coating of dendric carbosilane cores and used in a generally applicable one-pot reaction (Birch reduction in liquid ammonia and subsequent SN2 reaction) to generate a thioether linkage between the monosaccharide moieties and a carbosilane dendrimer. The dendrimers were uniformly functionalized with the monosaccharides in good yields. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(00)00247-0

文献信息

• Preparation and characterization of N-[2-(glycosyloxy)-ethyl]chitosan derivatives
  作者：Kevin R. Holme、Laurance D. Hall

  DOI：10.1016/s0008-6215(00)90502-0

  日期：1992.3

  the molar ratio of glycoside to free amine groups of chitosan by between 0.5 and 3.0. Derivatives of degree of substitution >0.3 were typically water soluble, and compounds of higher d.s. generally gave less-viscous aqueous solutions. Assignment of 13C-n.m.r. chemical shifts verified the structure of these derivatives. The linewidths of the branch resonances (5–100 Hz) provided qualitative information

  摘要制备并表征了8种单糖的烯丙基糖苷，包括1H-和13C-nmr分配。通过烯丙基糖苷的还原性臭氧分解获得的甲酰基甲基糖苷已被还原性N-烷基化为壳聚糖，典型收率为80％。α-和β-d-吡喃葡萄糖，α-和β-d-吡喃葡萄糖，2-乙酰氨基-2-脱氧-α-和β-d-吡喃葡萄糖，β-d-葡萄糖醛酸和β-乳糖的糖苷具有通过这种方法被合并。通过将壳聚糖的糖苷与游离胺基的摩尔比变化在0.5和3.0之间来控制产物的取代度（ds）。取代度> 0.3的衍生物通常是水溶性的，并且较高ds的化合物通常会产生粘度较低的水溶液。13C-nmr的分配 化学位移证实了这些衍生物的结构。分支共振的线宽（5–100 Hz）提供了有关ds与分支迁移率之间关系的定性信息。高ds产物的共振比类似的低ds衍生物更窄，更强烈。骨架的壳聚糖共振通常较宽（50-200 Hz），强度较低，因此难以完全分配。
• Stereoselective Syntheses of<i>α</i>-Glucuronides Using Dehydrative Glycosylation
  作者：Shinkiti Koto、Teruhisa Miura、Motoko Hirooka、Aya Tomaru、Mika Iida、Masanori Kanemitsu、Kazuhiro Takenaka、Shinichi Masuzawa、Saeko Miyaji、Naoko Kuroyanagi、Miki Yagishita、Shonosuke Zen、Kazuo Yago、Fumiya Tomonaga

  DOI：10.1246/bcsj.69.3247

  日期：1996.11

  Methyl and benzyl 2,3,4-tri-O-benzyl-d-glucopyranuronates, prepared from d-glucurono-6,3-lactone, afforded selectively the corresponding α-glucopyranosiduronates by the aid of the condensing reagent system composed of p-nitrobenzenesulfonyl chloride, silver trifluoromethanesulfonate, and triethylamine. Using this method, O-α-d-glucopyranuronosyl-(1→3)-O-α-l-arabinofuranosyl-(1→3)-d-xylopyranose, one of the minimal component units in the structure of plantago-mucilage A from the seeds of Plantago asiatica Linné constituting a Chinese medicine : chegianzi [].

  在对硝基苯磺酰氯、三氟甲磺酸银和三乙胺组成的缩合试剂体系的帮助下，由 d-葡萄糖醛酸-6,3-内酯制备的 2,3,4-三-O-苄基-d-吡喃葡萄糖醛酸甲酯和苄酯选择性地得到了相应的 α-吡喃葡萄糖苷酸盐。利用这种方法，从构成中药车前子的车前子种子中提取出了车前子粘液 A 结构的最小组成单位之一--O-α-d-吡喃葡萄糖呋喃糖基-(1→3)-O-α-阿拉伯呋喃糖基-(1→3)-d-吡喃木糖[]。
• Phenylenediamine-based bivalent glycocyclophanes: synthesis and analysis of the influence of scaffold rigidity and ligand spacing on lectin binding in cell systems with different glycomic profiles
  作者：Sabine André、Trinidad Velasco-Torrijos、Rosaria Leyden、Sebastien Gouin、Manuela Tosin、Paul V. Murphy、Hans-Joachim Gabius

  DOI：10.1039/b913010a

  日期：——

  The conjugation of carbohydrates to synthetic scaffolds has the goal of preparing potent inhibitors of lectin binding. We herein report the synthesis of a panel of bivalent compounds (cyclophane and terephthalamide-derivatives) then used to establish the influence of scaffold flexibility on respective inhibitory potency in a medically relevant test system. Synthetic routes to two phenylenediamine-based glycocyclophanes involving Ugi reactions of glucuronic acid derivatives and subsequent ring closing metathesis are described, as are improvements for producing terephthalamide-based carbohydrate carriers. Assays were performed with human tumour cells measuring quantitatively the influence of the test compounds on fluorescent surface staining by labelled lectins. Biological evaluation using two different lines of cancer cells as well as cells with known alterations in the glycomic profile (cells treated with an inhibitor of glycan processing and a glycosylation mutant) reduced the risk of generating premature generalizations regarding inhibitor potency. Bioactivity relative to free mannose was invariably determined for the synthetic compounds. A clear trend for enhanced inhibitory properties for macrocyclic compounds compared to non-macrocyclic derivatives was discerned for one type of glycocyclophane. Herein we also document the impact of altering the spacing between the mannose residues, altering cell surface ligand density and cell-type reactivity. The applied strategy for the cell assays is proposed to be of general importance in the quest to identify medically relevant lectin inhibitors.

  将碳水化合物与合成支架共轭的目的是制备有效的凝集素结合抑制剂。我们在此报告了一组二价化合物（环烷和对苯二甲酰胺-衍生物）的合成过程，然后用来确定支架的灵活性在医学相关测试系统中对各自抑制效力的影响。文中介绍了两种苯二胺基糖环烷的合成路线，包括葡萄糖醛酸衍生物的乌基反应和随后的闭环偏析，以及生产对苯二甲酰胺基碳水化合物载体的改进方法。用人类肿瘤细胞进行了试验，定量测量了试验化合物对标记凝集素荧光表面染色的影响。使用两种不同的癌细胞系以及已知糖型改变的细胞（使用糖加工抑制剂和糖基化突变体处理的细胞）进行生物评估，降低了过早概括抑制剂效力的风险。合成化合物相对于游离甘露糖的生物活性始终是确定的。与非大环衍生物相比，一种类型的糖环烷明显具有增强大环化合物抑制性的趋势。在此，我们还记录了改变甘露糖残基间距、改变细胞表面配体密度和细胞类型反应性的影响。我们提出的细胞试验应用策略在寻找医学相关凝集素抑制剂的过程中具有普遍意义。
• X-Ray diffraction and high resolution NMR analysis of methyl d-glucopyranuronate derivatives
  作者：Anna Trynda、Janusz Madaj、Antoni Konitz、Andrzej Wiśniewski

  DOI：10.1016/s0008-6215(00)00157-9

  日期：2000.10

  X-Ray diffraction and high resolution H-1 and C-13 NMR spectral data for methyl 2,3,4,-tri-O-acetyl-alpha-D-glucopyranuronate and methyl (allyl 2,3,4-tri-O-acetyl-beta-D-glucopyranosid)uronate are presented. Both compounds adopt the C-4(1) conformation. (C) 2000 Elsevier Science Ltd. All rights reserved.