methyl 2-azido-2-deoxy-3,6-di-O-benzyl-β-D-glucopyranoside | 354986-34-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-azido-2-deoxy-3,6-di-O-benzyl-β-D-glucopyranoside
• 英文别名: methyl 2-azido-3,6-di-O-benzyl-2-deoxy-β-D-glucopyranoside；(2R,3S,4R,5R,6R)-5-azido-6-methoxy-4-phenylmethoxy-2-(phenylmethoxymethyl)oxan-3-ol
• CAS: 354986-34-8
• 化学式: C₂₁H₂₅N₃O₅
• 分子量: 399.447
• InChiKey: VZMHLEUVUOIBDE-PFAUGDHASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  29
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 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-2-deoxy-3,6-di-O-benzyl-β-D-glucopyranoside 在 吡啶 、 二苯基亚砜 、 palladium on activated carbon 、 氢气 、 溶剂黄146 、 硫代乙酸 、 2,4,6-三叔丁基嘧啶 作用下， 以 甲醇 、 二氯甲烷 为溶剂， -78.0~20.0 ℃ 、101.33 kPa 条件下， 反应 21.0h， 生成 methyl 4-O-(2-deoxy-2-fluoro-β-D-galactopyranosyl)-2-acetamido-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  选择性脱氧氟化 N-乙酰乳糖胺类似物作为 19F NMR 探针研究碳水化合物-半乳糖凝集素相互作用

  摘要：

  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

  DOI：

  10.1002/chem.202101752
• 作为产物：
  描述：

  甲基 3,6-二-O-苄基-2-脱氧-2-(1,3-二氧代-1,3-二氢-2H-异吲哚-2-基)吡喃己糖苷 在 4-二甲氨基吡啶 、 triflic azide 、 乙二胺 作用下， 以 甲醇 、 二氯甲烷 、 乙腈 、 Petroleum ether 为溶剂， 反应 17.0h， 生成 methyl 2-azido-2-deoxy-3,6-di-O-benzyl-β-D-glucopyranoside
  参考文献：
  名称：

  选择性脱氧氟化 N-乙酰乳糖胺类似物作为 19F NMR 探针研究碳水化合物-半乳糖凝集素相互作用

  摘要：

  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

  DOI：

  10.1002/chem.202101752

文献信息

• Direct and stereoselective synthesis of β-d-mannosides using 4,6-O-benzylidene-protected mannosyl diethyl phosphite as a donor
  作者：Toshifumi Tsuda、Ryoichi Arihara、Shinya Sato、Miyuki Koshiba、Seiichi Nakamura、Shunichi Hashimoto

  DOI：10.1016/j.tet.2005.08.090

  日期：2005.11

  A direct and practical method for the construction of β-mannosidic linkages is described. While β-selectivities in the TMSOTf-promoted glycosidation of 2,3,4,6-tetra-O-benzyl-d-mannosyl diethyl phosphite are found to be highly dependent on the reactivity of acceptor alcohols, 2,3-di-O-benzyl-4,6-O-benzylidene-d-mannosyl diethyl phosphite reacts with a wide range of acceptor alcohols in the presence

  描述了构建β-甘露糖苷键的直接和实用的方法。虽然发现在TMSOTf促进的2,3,4,6-四-O-苄基-d-甘露糖基亚磷酸二乙酯的糖基化反应中的β选择性高度依赖于受体醇的反应性，但2,3-二-O亚甲基-苄基-4,6- O-亚苄基-d-甘露糖基二乙基酯在TMSOTf存在下于-45°C在CH 2 Cl 2中与多种受体醇反应，以高收率得到β-甘露糖苷高β选择性。
• Synthesis and unexpected binding of monofluorinated N,Nʹ-diacetylchitobiose and LacdiNAc to wheat germ agglutinin
  作者：Martin Kurfiřt、Vojtěch Hamala、Jan Beránek、Lucie Červenková Šťastná、Jakub Červený、Martin Dračínský、Jana Bernášková、Vojtěch Spiwok、Zuzana Bosáková、Pavla Bojarová、Jindřich Karban

  DOI：10.1016/j.bioorg.2024.107395

  日期：2024.4

  Fluorination of carbohydrate ligands of lectins is a useful approach to examine their binding profile, improve their metabolic stability and lipophilicity, and convert them into F NMR-active probes. However, monofluorination of monovalent carbohydrate ligands often leads to a decreased or completely lost affinity. By chemical glycosylation, we synthesized the full series of methyl β-glycosides of

  凝集素碳水化合物配体的氟化是检查其结合特征、提高其代谢稳定性和亲脂性并将其转化为 F NMR 活性探针的有用方法。然而，单价碳水化合物配体的单氟化常常导致亲和力降低或完全丧失。通过化学糖基化，我们合成了全系列的 ,′-二乙酰壳二糖 (GlcNAcβ(1–4)GlcNAcβ1-OMe) 和 LacdiNAc (GalNAcβ(1–4)GlcNAcβ1-OMe) 的全系列甲基 β-糖苷，并在所有羟基位置上系统地单氟化。竞争性酶联凝集素测定表明，壳二糖苷 6' 位的氟化导致与麦芽凝集素 (WGA) 的亲和力前所未有地增加了一个数量级。我们首次表征了先前未充分研究的 WGA 配体 LacdiNAc 的结合特征。令人惊讶的是，4'-氟-LacdiNAc 与 WGA 的结合甚至比未修饰的 LacdiNAc 更强。使用分子动力学计算以及 STD 和转移的 NOESY NMR 技术对这些观察结果进行了解释，这为非还原性
• Why Are the Hydroxy Groups of Partially Protected <i>N</i>-Acetylglucosamine Derivatives Such Poor Glycosyl Acceptors, and What Can Be Done about It? A Comparative Study of the Reactivity of <i>N</i>-Acetyl-, <i>N</i>-Phthalimido-, and 2-Azido-2-deoxy-glucosamine Derivatives in Glycosylation. 2-Picolinyl Ethers as Reactivity-Enhancing Replacements for Benzyl Ethers
  作者：David Crich、Vadim Dudkin

  DOI：10.1021/ja010086b

  日期：2001.7.1

  Competition experiments were used to determine that the 4-OH of a 2-deoxy-2-azidoglucose derivative is more reactive than that of the corresponding N-phthalimido glucose derivative which, in turn, is more easily glycosylated than the N-acetyl derivative. Glycosylation of the C-OH groups of the N,N-diacetyl and N-acetyl-N-benzyl glucosamine was also found to be superior to that of the simple N-acetyl substance. The 3-O-picolinyl ether of a 4,6-O-benzylidene-protected N-acetylglucosamine was shown to have a strong intramolecular hydrogen bond to the adjacent acetamide group. This interaction does not persist in the 3-O-picolinyl-6-O-benzyl N-acetylglucosamine derivative. owing to a probable competing hydrogen bond between the 4-OH and the picolinyl ether. However, in the 3-O-picolinyl-4-O-benzyl N-acetylglucosamine regioisomer the picolinyl-acetamide hydrogen bond persists and leads to an enhancement of reactivity of the 6-OH, over and above that in the corresponding 3-O-benzyl ether. due to disruption of the typical intermolecular amide hydrogen bonding scheme. It is demonstrated that the picolinyl ether is readily removed by hydrogenolysis at atmospheric pressure and room temperature.
• A stereocontrolled construction of 2-azido-2-deoxy-1,2-trans-β-glycosidic linkages utilizing 2-azido-2-deoxyglycopyranosyl diphenyl phosphates
  作者：Toshifumi Tsuda、Seiichi Nakamura、Shunichi Hashimoto

  DOI：10.1016/s0040-4039(03)01557-0

  日期：2003.8

  A high-yielding and stereocontrolled construction of 2-azido-2-deoxy-1,2-trans-beta-glycosidic linkages has been achieved by exploiting TMSOTf-promoted 1,2-trans-glycosidation of 2-azido-2-deoxyglycopyranosyl diphenyl phosphates with various glycoside alcohols in propionitrile at -78degreesC. The present method exhibits the highest levels of 1,2-trans-beta-selectivity reported to date for this type of glycosidation. (C) 2003 Elsevier Ltd. All rights reserved.
• A highly stereoselective construction of 1,2-trans-β-glycosidic linkages capitalizing on 2-azido-2-deoxy-d-glycosyl diphenyl phosphates as glycosyl donors
  作者：Toshifumi Tsuda、Seiichi Nakamura、Shunichi Hashimoto

  DOI：10.1016/j.tet.2004.08.076

  日期：2004.11

  The scope of TMSOTf-promoted glycosidation of 2-azido-2-deoxyglycopyranosyl diphenyl phosphates is investigated. The 3,4,6-tri-O-benzyl-protected glucosyl and galactosyl donors and the 4,6-O-benzylidene-protected galactosyl donor each react with a range of acceptor alcohols in the presence of a stoichiometric amount of TMSOTf in propionitrile at -78 degreesC to afford 1,2-trans-beta-linked disaccharides in high yields with alpha:beta ratios ranging from 9:91 to 1: > 99, regardless of the anomeric composition of the donor used. The use of propionitrile as a solvent at -78 degreesC has proven to be among the best choice for the highest levels of beta-selectivity reported to date for this type of glycosidation. A plausible reaction mechanism, which features a large equilibrium preference for alpha-glycosyl-nitrilium ions over beta-nitrilium ions, is proposed based on byproducts formed through their intermediacy and accounts for the observed excellent beta-selectivities. (C) 2004 Elsevier Ltd. All rights reserved.