methyl 2,3,4-tri-O-benzoyl-6-O-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-β-D-galactopyranoside | 143292-66-4

• 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-6-O-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-β-D-galactopyranoside
• 英文别名: Bz(-2)[Bz(-3)][Bz(-4)][Bz(-6)]Glc(b1-6)[Bz(-2)][Bz(-3)][Bz(-4)]b-Gal1Me；[(2R,3R,4S,5R,6R)-3,4,5-tribenzoyloxy-6-[[(2R,3S,4S,5R,6R)-3,4,5-tribenzoyloxy-6-methoxyoxan-2-yl]methoxy]oxan-2-yl]methyl benzoate
• CAS: 143292-66-4
• 化学式: C₆₂H₅₂O₁₈
• 分子量: 1085.08
• InChiKey: LAUMDKJWUNYDOX-RVYSHGDDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.9
• 重原子数：
  80
• 可旋转键数：
  26
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  221
• 氢给体数：
  0
• 氢受体数：
  18

反应信息

• 作为反应物：
  描述：

  methyl 2,3,4-tri-O-benzoyl-6-O-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-β-D-galactopyranoside 在 zinc(II) chloride 作用下， 以 氯仿 为溶剂， 反应 3.0h， 以69%的产率得到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：

  benzoxazol-2-yl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranoside 在 吡啶 、 甲醇 、 氨 、 三氟甲烷磺酸甲酯 作用下， 反应 17.0h， 生成 methyl 2,3,4-tri-O-benzoyl-6-O-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-β-D-galactopyranoside
  参考文献：
  名称：

  S-苯并恶唑基在寡糖合成中作为稳定的保护基和有效的端基离开基团

  摘要：

  作为开发用于立体选择性糖基化和收敛性寡糖合成的新多功能构件的计划的一部分，我们证明了S-苯并恶唑基（SBox）糖苷对碳水化合物化学中采用的主要保护基操作稳定。另一方面，它们可以在相对温和的反应条件下被糖基化以提供1，2-反式或1，2-顺式连接的二糖。还证明了SBox部分的选择性和化学选择性活化是可行的，这通过合成许多寡糖序列得到证明。

  DOI：

  10.1021/jo071191s

文献信息

• <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。
• S-Thiazolinyl (STaz) Glycosides as Versatile Building Blocks for Convergent Selective, Chemoselective, and Orthogonal Oligosaccharide Synthesis
  作者：Papapida Pornsuriyasak、Alexei V. Demchenko

  DOI：10.1002/chem.200600262

  日期：2006.8.25

  In the aim of developing new procedures for efficient oligosaccharide assembly, a range of S-thiazolinyl (STaz) glycosides have been synthesized. These novel derivatives were evaluated against a variety of reaction conditions and were shown to be capable of being chemoselectively activated in the armed-disarmed fashion. Moreover, the S-thiazolinyl moiety exhibited a remarkable propensity for selective

  为了开发有效寡糖组装的新方法，已合成了一系列S-噻唑啉基（STaz）糖苷。这些新颖的衍生物针对各种反应条件进行了评估，并显示出能够以武装-解除武装的方式进行化学选择性活化。此外，与其他常见的离去基团相比，S-噻唑啉基部分显示出显着的选择性活化倾向。相反，可以在STaz部分上选择性激活各种离去基团，从而允许STaz / S-乙基和STaz / S-苯基正交方法。为了证明新型STaz衍生物的多功能性，已经以收敛的选择性，正交和化学选择性方式合成了许多寡糖靶标。
• Potent, Versatile, and Stable: Thiazolyl Thioglycosides as Glycosyl Donors
  作者：Alexei V. Demchenko、Papapida Pornsuriyasak、Cristina De Meo、Nelli N. Malysheva

  DOI：10.1002/anie.200454047

  日期：2004.6.7
• <i>S</i>-Benzoxazolyl as a Stable Protecting Moiety and a Potent Anomeric Leaving Group in Oligosaccharide Synthesis
  作者：Medha N. Kamat、Cristina De Meo、Alexei V. Demchenko

  DOI：10.1021/jo071191s

  日期：2007.8.31

  As a part of a program for developing new versatile building blocks for stereoselective glycosylation and convergent oligosaccharide synthesis, we demonstrated that S-benzoxazolyl (SBox) glycosides are stable toward major protecting group manipulations employed in carbohydrate chemistry. On the other hand, they can be glycosidated under relatively mild reaction conditions to afford either 1,2-trans

  作为开发用于立体选择性糖基化和收敛性寡糖合成的新多功能构件的计划的一部分，我们证明了S-苯并恶唑基（SBox）糖苷对碳水化合物化学中采用的主要保护基操作稳定。另一方面，它们可以在相对温和的反应条件下被糖基化以提供1，2-反式或1，2-顺式连接的二糖。还证明了SBox部分的选择性和化学选择性活化是可行的，这通过合成许多寡糖序列得到证明。
• 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
  作者：Thomas Ziegler、Heinz Sutoris、Cornelis P.J. Glaudemans

  DOI：10.1016/s0008-6215(00)90575-5

  日期：1992.5

  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).