methyl 2,3,4-tri-O-benzoyl-β-D-galactopyranoside | 53182-61-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,4-tri-O-benzoyl-β-D-galactopyranoside
• 英文别名: methyl-2,3,4-tri-O-benzoyl-β-D-galactoside；Methyl-(2,3,4-tri-O-benzoyl-β-D-galactopyranosid)；Methyl-(2,3,4-tri-O-benzoyl-galactopyranosid)；[(2R,3S,4S,5R,6R)-4,5-dibenzoyloxy-2-(hydroxymethyl)-6-methoxyoxan-3-yl] benzoate
• CAS: 53182-61-9
• 化学式: C₂₈H₂₆O₉
• 分子量: 506.509
• InChiKey: BHQKQQXWEXIQMI-RIFZOBPSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  37
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  118
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  methyl 2,3,4-tri-O-benzoyl-β-D-galactopyranoside 在 2,4,6-三甲基吡啶 、 silver trifluoromethanesulfonate 、 zinc(II) chloride 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 反应 3.0h， 生成 O-(2,3,4,6-Tetra-O-benzoyl-β-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzoyl-α-D-galactopyranosyl chloride
  参考文献：
  名称：

  Binding studies on internal immunodeterminants: synthesis of β-(1 → 6)-linked oligosaccharide methyl glycosides having one to four internal d-galactopyranosyl residues flanked by gentiobiose residues

  摘要：

  The oligosaccharide glycosides beta-D-Glc p-(1 --> 6)-beta-D-Glc p-(1 --> 6)-[beta-D-Gal p-(1 --> 6)]n-beta-D-Glc p-(1 --> 6)-beta-D-Glc p-1 --> OMe (n = 1-4) were prepared by a convergent block synthesis. Haloacetyl, tert-butyldiphenylsilyl, and dimethylthexylsilyl groups were used as temporary protective groups for the preparation of the intermediate glycosyl donors and acceptors. The deoxygenated trisaccharide glyco-sides beta-D-Glc p-(1 --> 6)-beta-D-Gal p-(1 --> 6)-4-deoxy-beta-D-xylo-Hex p-1 --> OMe and beta-D-Glc p-(1 --> 6)-4-deoxy-beta-D-xylo-Hex p-(1 --> 6)-beta-D-Gal p-1 --> OMe were also synthesized. The binding of each glycoside to the monoclonal antigalactan antibody IgA 1539 was studied and the results support the previous finding that J539 can bind to internal antigenic epitopes. The data are consistent with the interpretation that subsite C of that antibody binds glucose with a K(a) of approximately 6 (cf. 10.9 for galactose).

  DOI：

  10.1016/s0008-6215(00)90575-5
• 作为产物：
  描述：

  甲基-Β-D-吡喃半乳糖苷 在 吡啶 、 2,4,6-三甲基吡啶 、 硫脲 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 反应 4.5h， 生成 methyl 2,3,4-tri-O-benzoyl-β-D-galactopyranoside
  参考文献：
  名称：

  烷基六吡喃糖苷的选择性溴乙酰化：一种易于制备的中间体，用于合成（1 ---- 6）连接的寡糖。

  摘要：

  甲基β-D-半乳糖-（1），α-D-半乳糖-（6），β-D-葡萄糖-（18），（22）和α-D-甘露糖吡喃糖苷（31）的溴乙酰化作用，以及苄基β-D-吡喃葡萄糖苷（27）以50-60％的收率得到相应的6-O-溴乙酰基衍生物2、7、19、23、32和28。3-O-苄基-β-D-吡喃半乳糖苷的甲基溴乙酰化（11）提供了甲基3-O-苄基-6-O-溴乙酰基-β-D-吡喃半乳糖苷（12，60％）以及3-O-甲基苄基-2,6-二-O-溴乙酰基-β-D-吡喃半乳糖苷（13，14％）。将化合物2、7、19、23、32、28和12进行苯甲酰化，将得到的完全保护的衍生物用硫脲脱卤乙酰化，得到β-半乳糖的甲基2,3,4-三-O-苯甲酰基-D-吡喃葡萄糖苷（5），α-半乳糖（9），β-葡萄糖（21），α-葡萄糖（25）和α-甘露糖（34）以及苄基2,3，4-三-O-苯甲酰基-β-D-吡喃葡萄糖苷（30）和甲基3-O-苄基-2

  DOI：

  10.1016/0008-6215(89)85018-9

文献信息

• Mild and Chemoselective Deacetylation Method Using a Catalytic Amount of Acetyl Chloride in Methanol
  作者：B. Kim、Chang-Eun Yeom、So Lee、Young Kim

  DOI：10.1055/s-2005-869838

  日期：——

  Efficient deacetylation of alcohol acetates under mild acidic conditions was accomplished with a catalytic amount of acetyl chloride in methanol. Acetates of various primary, secondary, aromatic and sugar alcohols were successfully deprotected. Highly chemoselective removal of acetyl groups in presence of ­other commonly employed esters was also achieved in excellent yields. The reactivity of this transesterification-mediated deacetyl­ation was found to be directly dependent upon the electronic and steric nature of the acetates.

  在中等酸性条件下，使用催化量的乙酰氯在甲醇中实现了乙酸酯的高效脱乙酰化，成功地对各种伯醇、仲醇、芳香醇和糖醇的乙酸酯进行了脱保护。在其他常用酯存在的情况下，乙酰基的高选择性去除也以优异的产率实现。研究发现，这种通过酯交换介导的脱乙酰化反应的活性直接取决于乙酸酯的电子和立体性质。
• Selective bromoacetylation of alkyl hexopyranosides: A facile preparation of intermediates for the synthesis of (1→6)-linked oligosaccharides
  作者：Thomas Ziegler、Pavol Kováč、Cornelis P.J. Glaudemans

  DOI：10.1016/0008-6215(89)85018-9

  日期：1989.12

  (30) and methyl 3-O-benzyl-2,4-di-O-benzoyl-beta-D-galactopyranoside (15). These compounds can be used as nucleophiles for the synthesis of (1----6)-linked oligosaccharides. The conversion 1----5 could be performed without isolation of the intermediates. The treatment of bromoacetyl derivatives with benzoyl chloride in pyridine resulted in the benzoylation of the remaining free hydroxyl groups and the

  甲基β-D-半乳糖-（1），α-D-半乳糖-（6），β-D-葡萄糖-（18），（22）和α-D-甘露糖吡喃糖苷（31）的溴乙酰化作用，以及苄基β-D-吡喃葡萄糖苷（27）以50-60％的收率得到相应的6-O-溴乙酰基衍生物2、7、19、23、32和28。3-O-苄基-β-D-吡喃半乳糖苷的甲基溴乙酰化（11）提供了甲基3-O-苄基-6-O-溴乙酰基-β-D-吡喃半乳糖苷（12，60％）以及3-O-甲基苄基-2,6-二-O-溴乙酰基-β-D-吡喃半乳糖苷（13，14％）。将化合物2、7、19、23、32、28和12进行苯甲酰化，将得到的完全保护的衍生物用硫脲脱卤乙酰化，得到β-半乳糖的甲基2,3,4-三-O-苯甲酰基-D-吡喃葡萄糖苷（5），α-半乳糖（9），β-葡萄糖（21），α-葡萄糖（25）和α-甘露糖（34）以及苄基2,3，4-三-O-苯甲酰基-β-D-吡喃葡萄糖苷（30）和甲基3-O-苄基-2
• Stereoselective total syntheses of the naturally occurring enantiomers of N-acetylneuraminic acid and 3-deoxy-D-manno-2-octulosonic acid. A new and stereospecific approach to sialo and 3-deoxy-D-manno-2-octulosonic acid conjugates
  作者：Samuel J. Danishefsky、Michael P. DeNinno、Shu Hui. Chen

  DOI：10.1021/ja00220a035

  日期：1988.6

  Preparation de l'enantiomere naturel de l'acide N-acetyl neuraminique a partir du phenylseleno-2 propanal et du benzyloxy-4 [furyl-2]-1 methoxy-1 trimethylsiloxy-3 butadiene-«1,3». L'enantiomere du KDO est obtenu a partir du phenylseleno-2 propionate de methyle

  制备 de l'enantiomere naturel de l'acide N-乙酰神经氨酸 a partir du phenylseleno-2 propanal et du benzyloxy-4 [furyl-2]-1 methoxy-1 trimethylsiloxy-3 butadiene-«1,3»。L'enantiomere du KDO est obtenu a partir du phenylseleno-2 propionate demethyle
• Stereoselective 1,2-cis-galactosylation assisted by remote neighboring group participation and solvent effects
  作者：Alexei V. Demchenko、Emmanuel Rousson、Geert-Jan Boons

  DOI：10.1016/s0040-4039(99)01203-4

  日期：1999.9

  Iodonium-ion promoted glycosylations in 1,4-dioxane/toluene with galactosyl donors having an electron-donating neighboring group participating functionality at C-4 give exceptional high α-anomeric selectivities.

  碘鎓离子在1,4-二恶烷/甲苯中促进的糖基化反应以及在C-4上具有供电子的邻近基团参与官能团的半乳糖基供体赋予了极高的α-异头异构体选择性。
• <i>S</i>-Benzoxazolyl (SBox) Glycosides in Oligosaccharide Synthesis: Novel Glycosylation Approach to the Synthesis of β-<scp>d</scp>-Glucosides, β-<scp>d</scp>-Galactosides, and α-<scp>d</scp>-Mannosides
  作者：Alexei Demchenko、Medha Kamat、Cristina De Meo

  DOI：10.1055/s-2003-40345

  日期：——

  Per-acetylated and per-benzoylated S-benzoxazolyl (SBox) glycosides have been synthesized and applied to highly efficient 1,2-trans glycosylation. Complete stereoselectivities and remarkably high yields were achieved for the synthesis of β-d-glucosides, β-d-galactosides, and α-d-mannosides. It was also de­monstrated that benzoylated ‘disarmed’ SBox glycosides could be selectively activated in the presence of both armed and disarmed ethyl thioglycosides. Convergent synthesis of the tetra­saccharide β-d-Glc-(1-6)-β-d-Gal-(1-6)-β-d-GlcNAc-(1-6)-α-d-GlcOMe was achieved in three sequential selective glycosylation steps.

  合乙酰化和合苯甲酰化的S-苯并噁唑基(SBox)糖苷已被合成并应用于高效的1,2-反式糖苷化。对β-d-葡萄糖苷、β-d-半乳糖苷和α-d-甘露糖苷的合成实现了完全的立体选择性和显著高的产率。还证明了苯甲酰化的“去活化”SBox糖苷可以在有活化和去活化的乙硫糖苷同时存在的情况下被选择性激活。成功实现了四糖β-d-Glc-(1-6)-β-d-Gal-(1-6)-β-d-GlcNAc-(1-6)-α-d-GlcOMe的汇聚合成，通过三步连续的选择性糖苷化反应完成。