3,6-di-O-acetyl-2-azido-4-O-benzyl-2-deoxy-α-D-glucopyranosyl bromide | 67546-24-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,6-di-O-acetyl-2-azido-4-O-benzyl-2-deoxy-α-D-glucopyranosyl bromide
• 英文别名: [(2R,3S,4R,5R,6R)-4-acetyloxy-5-azido-6-bromo-3-phenylmethoxyoxan-2-yl]methyl acetate
• CAS: 67546-24-1
• 化学式: C₁₇H₂₀BrN₃O₆
• 分子量: 442.266
• InChiKey: FLKGPGBWRWGESB-HHARLNAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  27
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  85.4
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  3,6-di-O-acetyl-2-azido-4-O-benzyl-2-deoxy-α-D-glucopyranosyl bromide 在 2,4,6-三甲基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 16.08h， 生成 Acetic acid (2R,3S,4R,5R,6R)-2-acetoxymethyl-5-azido-3-benzyloxy-6-(3-bromo-4-methyl-2-oxo-2H-chromen-7-yloxy)-tetrahydro-pyran-4-yl ester
  参考文献：
  名称：

  α:β Selectivity in the synthesis of 3-substituted, 4-methyl umbelliferone glycosides of N-acetyl glucosamine and chitobiose

  摘要：

  The influence of phenolic acceptor nucleophilicity; for example, 3-substituted, 4-methylumbelliferones, and glycosyl donor electrophilicity; for example, 3- and 4-substituted N-acetylglucosamines, on glycosylation stereochemistry has been evaluated. In a systematic comparison, the stereochemical outcome as well as the reaction yield appeared to be influenced by the 3- and 4-substituents of the donor as well as the 3-substituent of the aryl acceptor. In the context of synthesizing a fluorogenic substrate for oligosaccharyltransferase, an alpha-glycoside was desired. Although most acceptor-donor pairs led to predominantly or exclusively the beta-glycoside, reaction of the most activated (3,4-di-O-benzyl) donor and the least nucleophilic acceptor (3-Br), resulted in a 1:1 ratio of alpha,beta arylglycosides. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.11.053
• 作为产物：
  描述：

  1,3,6-tri-O-acetyl-2-azido-2-deoxy-4-O-benzyl-D-glucopyranose 在 氢溴酸 作用下， 以 溶剂黄146 为溶剂， 反应 3.5h， 以100%的产率得到3,6-di-O-acetyl-2-azido-4-O-benzyl-2-deoxy-α-D-glucopyranosyl bromide
  参考文献：
  名称：

  α:β Selectivity in the synthesis of 3-substituted, 4-methyl umbelliferone glycosides of N-acetyl glucosamine and chitobiose

  摘要：

  The influence of phenolic acceptor nucleophilicity; for example, 3-substituted, 4-methylumbelliferones, and glycosyl donor electrophilicity; for example, 3- and 4-substituted N-acetylglucosamines, on glycosylation stereochemistry has been evaluated. In a systematic comparison, the stereochemical outcome as well as the reaction yield appeared to be influenced by the 3- and 4-substituents of the donor as well as the 3-substituent of the aryl acceptor. In the context of synthesizing a fluorogenic substrate for oligosaccharyltransferase, an alpha-glycoside was desired. Although most acceptor-donor pairs led to predominantly or exclusively the beta-glycoside, reaction of the most activated (3,4-di-O-benzyl) donor and the least nucleophilic acceptor (3-Br), resulted in a 1:1 ratio of alpha,beta arylglycosides. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.11.053

文献信息

• Palladium(<scp>ii</scp>)-assisted activation of thioglycosides
  作者：Samira Escopy、Yashapal Singh、Alexei V. Demchenko

  DOI：10.1039/d1ob00004g

  日期：——

  Described herein is the first example of glycosidation of thioglycosides in the presence of palladium(II) bromide. While the activation with PdBr2 alone was proven feasible, higher yields and cleaner reactions were achieved when these glycosylations were performed in the presence of propargyl bromide as an additive. Preliminary mechanistic studies suggest that propargyl bromide assists the reaction

  本文描述的是在溴化钯( II )存在下硫代糖苷的糖苷化的第一个实例。虽然单独使用 PdBr 2进行活化已被证明是可行的，但当这些糖基化在炔丙基溴作为添加剂存在的情况下进行时，可以实现更高的产率和更清洁的反应。初步机理研究表明，炔丙基溴通过产生电离络合物来促进反应，从而加速离去基团的离开。研究了与不同糖基受体反应的各种硫代糖苷供体，以确定这种新反应的初始范围。还探索了硫代糖苷相对于其他离去基团的选择性和化学选择性激活。
• Synthesis of heparin fragments. A chemical synthesis of the trisaccharide O-(2-deoxy-2-sulfamido-3,6-di-O-sulfo-α-d-glucopyranosyl)-(1→4)-O-(2-O-sulfo-α-l-idopyranosyluronic acid)-(1→4)-2-deoxy-2-sulfamido-6-O-sulfo-d-glucopyranose heptasodium salt
  作者：Jean-Claude Jacquinet、Maurice Petitou、Philippe Duchaussoy、Isidore Lederman、Jean Choay、Giangiacomo Torri、Pierre Sinaÿ

  DOI：10.1016/0008-6215(84)85281-7

  日期：1984.7

  -acetyl-2-azido-4- O -benzyl-2-deoxy-α- d -glucopyranosyl)-(1→4)- O -(methyl 2- O -acetyl-3- O -benzyl-α- l -idopyranosyluronate)-(1→4)-6- O -acetyl-3- O -benzyl-2-(benzyloxycarbonyl)amino-2-deoxy-α- d - glucopyranoside in 88% yield. O -Deacetylation with sodium hydroxide, followed successively by O -sulfation in N,N -dimethylformamide in the presence of sulfur trioxide-trimethylamine complex, catalytic

  摘要首先将已知的3-O-苄基-1,2-O-异亚丙基-α-d-葡萄糖基呋喃糖转化为3-O-苄基-1,2-O-异亚丙基-β-1-基呋喃醛酸甲酯。酸水解，然后乙酰化并用四溴化钛处理，得到（2,4-二-O-乙酰基-3-O-苄基-α-1-吡喃吡喃基溴化）甲基脲酸酯，其立即被转化为4-O-甲基。乙酰基-3-O-苄基-β-1-氨基吡喃二酸酯1,2-（原乙酸叔丁酯）。用4-O-氯乙酰基进行两步取代4-O-乙酰基得到关键的衍生物结晶结晶3-O-苄基-4-O-氯乙酰基-β-1-氨基吡喃醛酸酯1,2-（叔-原乙酸正丁酯）。该原酸酯与过量的苄基6-O-乙酰基-3-O-苄基-2-（苄氧基羰基）氨基-2-脱氧-α-d-吡喃葡萄糖苷结晶在氯苯存在下缩合2，6-二甲基吡啶鎓高氯酸盐得到结晶的苄基6-O-乙酰基-3-O-苄基-2-（苄氧基羰基）氨基-2-脱氧-4-O-（甲基2-O-乙酰基-3-O-苄基-4- O-氯乙酰基-
• Syntheses of heparin - like pentamers containing “opened” uronic acid moieties
  作者：H. Lucas、J.E.M. Hasten、Th.G. van Dinther、D.G. Meuleman、S.F. van Aelst、C.A.A. van Boeckel

  DOI：10.1016/s0040-4020(01)81477-0

  日期：——
• Boeckel, C. A. A. van; Beetz, T., Recueil des Travaux Chimiques des Pays-Bas, 1985, vol. 104, # 6, p. 174 - 176
  作者：Boeckel, C. A. A. van、Beetz, T.

  DOI：——

  日期：——
• CHOAY, J.;JACQUINET, J. -C.;PETITOU, M.;SINAY, P.
  作者：CHOAY, J.、JACQUINET, J. -C.、PETITOU, M.、SINAY, P.

  DOI：——

  日期：——