| 176300-27-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• CAS: 176300-27-9
• 化学式: C₈₂H₈₆O₁₆
• 分子量: 1327.58
• InChiKey: MRAHZFGDSWYLQM-WYGAHWLESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.64
• 重原子数：
  98.0
• 可旋转键数：
  32.0
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  147.68
• 氢给体数：
  0.0
• 氢受体数：
  16.0

反应信息

• 作为反应物：
  描述：

  在 盐酸 、 3 A molecular sieve 、 sodium cyanoborohydride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 1.0h， 以88%的产率得到(2R,3R,4S,5R,6R)-4,5-Bis-benzyloxy-2-benzyloxymethyl-6-[(2R,3R,4S,5R,6S)-4,5-bis-benzyloxy-2-benzyloxymethyl-6-((2R,3R,4S,5R,6S)-4,5-bis-benzyloxy-2-benzyloxymethyl-6-methoxy-tetrahydro-pyran-3-yloxy)-tetrahydro-pyran-3-yloxy]-tetrahydro-pyran-3-ol
  参考文献：
  名称：

  Synthetic α,β-(1→4)-Glucan Oligosaccharides as Models for Heparan Sulfate. Part II.

  摘要：

  alpha,beta-(1-->4)-Glucan oligosaccharides were prepared as models for heparan sulfate with the simplifying assumptions that carboxyl-reduction and sulfation of heparan sulfate does not decrease the SMC antiproliferative activity and that N-sulfates in glucosamines can be replaced by O-sulfates. The target saccharides were synthesized using maltosyl building blocks. Glycosylation of methyl 2,3,6-tri-O-benzyl-alpha-D-glucopyranoside (1) with hepta-O-acetyl-alpha-maltosyl bromide (2) furnished trisaccharide 3 which was deprotected to alpha-D-Glc-(1-->4)-beta-D-Glc-(1-->4)-alpha-D-Glc(1 --> OCH3) (5) or, alternatively, converted to the trisaccharide glycosyl acceptor (8) with one free hydroxyl function (4''-OH). Further silver triflate mediated glycosylation with glucosyl or maltosyl bromide followed by deblocking gave the tetrasaccharide beta-D-Glc-(1-->4)-alpha-D-Glc-(1-->4)-beta-D-Glc-(1-->4)-alpha-D-(1-->OCH3) (11) and the pentasaccharide [alpha-D-Glc-(1-->4)-beta-D-Glc-(1-->4)-alpha-D-Glc-(1-->OCH3) (14). The trisaccharides 3, 4, 6, and 8 as well as pentasaccharide 12 were fully characterized by H-1, 3, 8 and 12 also by C-13 NMR spectroscopy. Assignments were possible using 1D TOCSY, in some cases supplemented by 2D T-ROESY, H-1,H-1 2D COSY, and H-1-detected one-bond and multiple-bond H-1,C-13 2D COSY experiments.

  DOI：

  10.1080/07328309608005439
• 作为产物：
  描述：

  (2R,3R,4S,5S,6R)-2-[(2R,3S,4R,5R,6S)-6-((2R,3R,4S,5R,6S)-4,5-Bis-benzyloxy-2-benzyloxymethyl-6-methoxy-tetrahydro-pyran-3-yloxy)-4,5-dihydroxy-2-hydroxymethyl-tetrahydro-pyran-3-yloxy]-6-hydroxymethyl-tetrahydro-pyran-3,4,5-triol 在 sodium hydride 、 zinc(II) chloride 作用下， 以 二甲基亚砜 为溶剂， 反应 22.0h， 生成
  参考文献：
  名称：

  Synthetic α,β-(1→4)-Glucan Oligosaccharides as Models for Heparan Sulfate. Part II.

  摘要：

  alpha,beta-(1-->4)-Glucan oligosaccharides were prepared as models for heparan sulfate with the simplifying assumptions that carboxyl-reduction and sulfation of heparan sulfate does not decrease the SMC antiproliferative activity and that N-sulfates in glucosamines can be replaced by O-sulfates. The target saccharides were synthesized using maltosyl building blocks. Glycosylation of methyl 2,3,6-tri-O-benzyl-alpha-D-glucopyranoside (1) with hepta-O-acetyl-alpha-maltosyl bromide (2) furnished trisaccharide 3 which was deprotected to alpha-D-Glc-(1-->4)-beta-D-Glc-(1-->4)-alpha-D-Glc(1 --> OCH3) (5) or, alternatively, converted to the trisaccharide glycosyl acceptor (8) with one free hydroxyl function (4''-OH). Further silver triflate mediated glycosylation with glucosyl or maltosyl bromide followed by deblocking gave the tetrasaccharide beta-D-Glc-(1-->4)-alpha-D-Glc-(1-->4)-beta-D-Glc-(1-->4)-alpha-D-(1-->OCH3) (11) and the pentasaccharide [alpha-D-Glc-(1-->4)-beta-D-Glc-(1-->4)-alpha-D-Glc-(1-->OCH3) (14). The trisaccharides 3, 4, 6, and 8 as well as pentasaccharide 12 were fully characterized by H-1, 3, 8 and 12 also by C-13 NMR spectroscopy. Assignments were possible using 1D TOCSY, in some cases supplemented by 2D T-ROESY, H-1,H-1 2D COSY, and H-1-detected one-bond and multiple-bond H-1,C-13 2D COSY experiments.

  DOI：

  10.1080/07328309608005439

文献信息

• [EN] A HIGHLY EFFICIENT GLYCOSYLATION CHEMISTRY ENABLED BY A DIRECTING-GROUP THAT IS PART OF THE ANOMERIC LEAVING-GROUP<br/>[FR] CHIMIE DE GLYCOSYLATION HAUTEMENT EFFICACE ACTIVÉE PAR UN GROUPE DIRECTEUR FAISANT PARTIE DU GROUPE PARTANT ANOMÉRIQUE
  申请人：UNIV CALIFORNIA

  公开号：WO2022165224A1

  公开（公告）日：2022-08-04

  Broadly applicable and stereoselective formation of glycosidic linkage remains challenging yet of critical importance in giycoscience. By developing an SN2 glycosylation, this work advances a general solution to this challenge via stereoinversion at the anomeric position of glycosyl ester donors. This SN2 process is enabled by a basic directing-group in the leaving-group, which is activated by a cationic gold catalyst or any other electrophilic reagent. Unlike all the reported directing group approaches, this strategy is applicable to any glycosyl donors - a long sought-after yet unmet goal in carbohydrate chemistry; moreover, the basic directing-group upon glycosylation is lost as part of the leaving-group and hence traceless in the glycoside products, therefore avoiding potential complications in downstream transformations. Highly selective construction of glycosidic bonds including challenging 1,2-cis glycosidic bonds is achieved in excellent yields. The strategy is applied iteratively to access oligosaccharides and can distinguish alcohols with different steric hindrance.

  广泛适用且立体选择性的糖苷键形成仍然具有挑战性，但在糖科学中至关重要。通过开发SN2糖基化，本研究通过糖酯供体的异构反转在糖基位置上推进了对这一挑战的普遍解决方案。此SN2过程由离去基中的碱性定向基启用，该定向基由阳离子金催化剂或任何其他亲电试剂激活。与所有报道的定向基方法不同，该策略适用于任何糖基供体-这是糖化学中一直追求但未能达成的目标；此外，糖基化后的碱性定向基将作为离去基的一部分而丢失，并且在糖苷产物中没有痕迹，因此避免了下游转化中的潜在复杂性。高度选择性的糖苷键构建，包括具有挑战性的1,2-顺式糖苷键，以极高的收率实现。该策略被迭代应用于访问寡糖，并且可以区分不同立体障碍的醇。