4’-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2’,3’,6’-tri-O-acetyl-D-glucopyranose | 18464-08-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4’-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2’,3’,6’-tri-O-acetyl-D-glucopyranose
• 英文别名: 2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl-(1->4),2,3,6-tri-O-acetyl-α-D-glucopyranose；2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-acetyl-α-D-glucopyranose；4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2,3,6-tri-O-acetyl-α-D-glucopyranose；2,3,6,2',3',4',6'-Hepta-O-acetyl-α-lactose；Gal2Ac3Ac4Ac6Ac(b1-4)a-Glc2Ac3Ac6Ac；[(2R,3R,4S,5R,6S)-4,5-diacetyloxy-6-hydroxy-3-[(2S,3R,4S,5S,6R)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxyoxan-2-yl]methyl acetate
• CAS: 18464-08-9；66073-13-0；71623-44-4；101981-29-7；109922-72-7；132287-75-3；132287-76-4；132287-78-6；132303-63-0；134311-82-3；134333-39-4；109922-73-8
• 化学式: C₂₆H₃₆O₁₈
• 分子量: 636.561
• InChiKey: QBBPOGFLHMTZQB-NDMRNNIMSA-N

物化性质

• 沸点：
  667.0±55.0 °C(Predicted)
• 密度：
  1.39±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.3
• 重原子数：
  44
• 可旋转键数：
  18
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  232
• 氢给体数：
  1
• 氢受体数：
  18

反应信息

• 作为反应物：
  描述：

  4’-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2’,3’,6’-tri-O-acetyl-D-glucopyranose 在 三氟甲磺酸三甲基硅酯 sodium methylate 、 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 生成 3-methoxycarbonylpropyl O-β-D-galactopyranosyl-(1->4)-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of multivalent β-lactosyl clusters as potential tumor metastasis inhibitors

  摘要：

  A beta-lactosyl residue was linked to the amino groUpS Of L-lysyl-L-lysine through spacer arms of three different lengths (C2, C4, and C-9) to give trivalent beta-lactosyl clusters in order to increase the inhibitory activity of the beta-lactosyl group against tumor cell colonization. Thus, O-(2,3,4,6-tetra-0-acetyl-beta-D-galactopyranosyl)-(1 --> 4)-2,3,6-tri-O-acetyl-glucopyranosyl trichloroacetimidate was treated with methyl or benzyl hydroxyethanoate, methyl or benzyl 4-hydroxybutanoate, and methyl 9-hydroxynonanoate, respectively, in the presence of trimethylsilyl trifluoromethanesulfonate to give the corresponding beta-lactosides. These were coupled to L-lysyl-L-lysine, after conversion to the N-hydroxysuccinimide esters, to yield the corresponding trivalent beta-lactosyl-L-lysyl-L-lysine conjugates in good yields. The beta-lactosyl group with a C4 spacer arm was also coupled similarly to poly(L-lysine) (M(r) 3800) to form a polyvalent beta-lactosyl cluster. Coinjection of the trivalent (with C2 and C4 spacer arms) and polyvalent beta-lactosyl clusters with the highly metastatic B16 murine melanoma cells inhibited the formation of lung colonies in C57/BL mice, whereas the trivalent cluster with a C-9 spacer arm displayed no activity.

  DOI：

  10.1016/0008-6215(93)80071-l
• 作为产物：
  描述：

  3,6,2',3',4',6'-Hexa-O-acetyl-1,2-O-(ethyl orthoacetyl)-α-lactose 在 palladium on activated charcoal 甲酸 、 氢气 、 silver(l) oxide 作用下， 以 甲醇 为溶剂， 25.0 ℃ 、420.58 kPa 条件下， 反应 33.75h， 生成 4’-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-2’,3’,6’-tri-O-acetyl-D-glucopyranose
  参考文献：
  名称：

  Synthesis and characterization of 6-O-β-lactosyl-α,β-d-mannopyranoses and 2,6-di-O-β-lactosyl-α,β-d-manno-pyranoses

  摘要：

  The reaction of 2,3,6,2',3',4',6'-hepta-O-acetyl-alpha-lactosyl bromide (4) and benzyl 3,4-di-O-benzyl-alpha-D-mannopyranoside (3) in the presence of mercury(II) cyanide in benzene-nitromethane produced benzyl 3,4-di-O-benzyl-2,6-bis-O-(2,3,6,2',3',4',6'-hepta-O-acetyl-beta-lactosyl)-alpha-D-mannopyranoside (5) and benzyl 3,4-di-O-benzyl-6-O-(2,3,6,2',3',4',6'-hepta-O-acetyl-beta-lactosyl)-alpha-D-mannopyranoside (6), as part of a complex mixture. Column chromatography, followed by acetylation of the fraction containing 5 and 6, gave a sample of 5 and benzyl 2-O-acetyl-3,4-di-O-benzyl-6-O-(2,3,6,2',3',4',6'-hepta-O-acetyl-beta-lactosyl)-alpha-D-mannopyranoside (7) in approximately 35% and 17% yields (based on 4), respectively. Deprotection of 5 and 7 afforded the target compounds, namely 2,6-di-O-beta-lactosyl-alpha,beta-D-mannopyranoses and 6-O-beta-lactosyl-alpha,beta-D-mannopyranoses, respectively. If the coupling of 4 with 3 were performed in the presence of silver trifluoromethanesulfonate and 2,4,6-trimethylpyridine, only a mixture of 3,6,2',3',4',6'-hexa-O-acetyl-alpha-lactose-1,2-{[3,6, 2',3',4',6'-hexa-O-acetyl-alpha-lactose 1,2-(benzyl 3,4-di-O-benzyl-alpha-D-mannopyranosid-6-yl orthoacetyl)-2-yl] orthoacetate} and 3,6,2',3',4',6'-hexa-O-acetyl-alpha-lactose 1,2-(benzyl 3,4-di-O-benzyl-alpha-D-mannopyranosid-6-yl orthoacetate) was obtained. The orthoacetates were characterized by n.m.r. spectroscopy. The two target materials are useful in the assessment of the binding properties of galactose-terminated ligands to the asialoglycoprotein receptor of normal rabbit and human hepatocytes.

  DOI：

  10.1016/0008-6215(91)89042-e

文献信息

• Selective anomeric deacetylation using zinc acetate as catalyst
  作者：Eda Kaya、Fatih Sonmez、Mustafa Kucukislamoglu、Mehmet Nebioglu

  DOI：10.2478/s11696-012-0143-5

  日期：2012.1.1

  alternative method has been developed for the anomeric deacetylation of fully acetylated carbohydrate derivatives using zinc acetate dihydrate as a catalyst in methanol under mild conditions. The experimental simplicity, low cost, acceptable yield, use of a readily handled acidic catalyst, and the environmentally benign nature are some of the advantages of this method.

  已经开发了另一种方法，用于在温和条件下使用乙酸锌二水合物作为催化剂在甲醇中将完全乙酰化的碳水化合物衍生物进行异头脱乙酰化。实验的简便性，低成本，可接受的产率，使用易于处理的酸性催化剂以及环境友好的性质是该方法的一些优点。
• Hafnium(IV) triflate as a potent catalyst for selective 1-O-deacetylation of peracetylated saccharides
  作者：Rui Wang、Ji-Zong Chen、Xiu-An Zheng、Rui Kong、Shan-Shan Gong、Qi Sun

  DOI：10.1016/j.carres.2017.11.015

  日期：2018.1

  An efficient method for selective anomeric deacetylation of peracetylated mono-, di-, and trisaccharides has been developed by using 2 mol% Hf(OTf)4 as catalyst in acetonitrile. Employment of ultrasonic irradiation could significantly accelerate the reaction rate. Mechanistic study confirmed the hydrolysis nature of this reaction, and NMR experimental data suggested that multiple peracetylated saccharide

  通过使用2 mol％的Hf（OTf）4作为乙腈中的催化剂，已经开发出一种有效的方法，用于将过乙酰化的单糖，二糖和三糖选择性异头脱乙酰。超声辐射的使用可以显着加快反应速度。机理研究证实了该反应的水解性质，NMR实验数据表明，多个过乙酰化的糖分子可能主要通过异头乙酸酯与Hf（IV）阳离子连接，从而促进其特异性水解。
• Sequential Dy(OTf)₃-Catalyzed Solvent-Free Per-<i>O</i>-Acetylation and Regioselective Anomeric De-<i>O</i>-Acetylation of Carbohydrates
  作者：Yi-Ling Yan、Jiun-Rung Guo、Chien-Fu Liang

  DOI：10.1002/asia.201700867

  日期：2017.9.19

  regioselective anomeric de‐O‐acetylation of carbohydrates can be tuned by adjusting the reaction medium. In this study, the per‐O‐acetylation of unprotected sugars by using a near‐stoichiometric amount of acetic anhydride under solvent‐free conditions resulted in the exclusive formation of acetylated saccharides as anomeric mixtures, whereas anomeric de‐O‐acetylation in methanol resulted in a moderate‐to‐excellent

  镝（III）三氟甲磺酸催化的per- ö -acetylation和区域选择性的端基异构脱ö碳水化合物-acetylation可以通过调节反应介质进行调谐。在这项研究中，在无溶剂条件下，通过使用接近化学计量的乙酸酐对未保护的糖进行过O-乙酰化，导致乙酰化糖类作为异头混合物独家形成，而异头De- O在甲醇中进行乙酰化可产生中等至优异的收率。与各种未保护的单糖或二糖的反应，然后半单步顺序转化为相应的乙酰化糖基半缩醛，也可导致高收率。此外，在Dy（OTf）3催化的糖基化反应后，获得的半缩醛可以成功转化为三氯亚氨酸盐。
• Regioselective Deprotection of Peracetylated Disaccharides at the Primary Position Catalyzed by Immobilized Acetyl Xylan Esterase from Bacillus pumilus
  作者：Teodora Bavaro、Marco Filice、Paolo Bonomi、Qais Abu alassal、Giovanna Speranza、Jose M. Guisan、Marco Terreni

  DOI：10.1002/ejoc.201100944

  日期：2011.11

  In this work peracetylated lactose and related compounds have been tested as advanced intermediate substrates in enzymatic deprotections catalyzed by acetyl xylan esterase (AXE) from Bacillus pumilus. In particular, we present a simple and efficient enzymatic procedure to obtain products bearing only one free primary hydroxy group in the C6′ position of the galactoside moiety of “lacto” carbohydrates

  在这项工作中，全乙酰化乳糖和相关化合物已被测试为高级中间底物，用于由来自短小芽孢杆菌的乙酰木聚糖酯酶 (AXE) 催化的酶促脱保护。特别是，我们提出了一种简单有效的酶促程序，以获得在“乳”碳水化合物的半乳糖苷部分的 C6' 位置仅带有一个游离伯羟基的产物。特别是，在 1-O-甲基乳糖胺和六乙酰乳醛的水解中取得了良好的产率（60-70%）。获得的产品作为用于合成非常重要的生物相关寡糖的高级构建模块引起了极大的兴趣。
• Effect of distal sugar and interglycosidic linkage of disaccharides on the activity of proline rich antimicrobial glycopeptides
  作者：Deepti S. Lele、Rohini Dwivedi、Saroj Kumari、Kanwal J. Kaur

  DOI：10.1002/psc.2826

  日期：2015.11

  drosocin analogs were compared with their corresponding monoglycosylated forms, β‐d‐glucosyl‐formaecin I and β‐d‐glucosyl‐drosocin, respectively. We observed neither major secondary structural alterations studied by circular dichroism nor substantial differences in the toxicity with mammalian cells among all of these analogs. The comparative analyses of antibacterial activities of these analogs of formaecin

  糖基化对蛋白质结构和功能的影响取决于多种内在因素，包括聚糖链长度。我们分析了远端糖和二糖的糖苷间键对富含脯氨酸的抗菌糖肽，福美霉素I和drosocin的特性的影响。它们的糖基化类似物带有乳糖，麦芽糖和纤维二糖，作为保守的苏氨酸残基上的聚糖侧链，是合成的，这些二糖具有相同的近端糖，并且远端糖和/或糖苷间键的性质各不相同。将这些含二糖的福美霉素I和drosocin类似物的结构和功能特性与其相应的单糖基化形式β - d-葡萄糖基-福美霉素I和β - d-葡萄糖基-drosocin。我们没有观察到通过圆二色性研究的主要的二级结构改变，也没有观察到所有这些类似物对哺乳动物细胞的毒性的实质性差异。对这些福美霉素I和drosocin类似物的抗菌活性的比较分析表明，β - d-麦芽糖基-福尔霉素I和β - d-麦芽糖基-drosocin比各自的β - d -Glc-类似物，β - d更有效-cellobiosyl-analog和β