methyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-β-D-glucopyranosyl-(1→4)-2,3,6-tri-O-benzyl-α-D-glucopyranose | 176169-13-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-β-D-glucopyranosyl-(1→4)-2,3,6-tri-O-benzyl-α-D-glucopyranose
• CAS: 176169-13-4
• 化学式: C₅₄H₆₆O₂₃
• 分子量: 1083.1
• InChiKey: OTIFAGKJDILQMW-GBAZOGDYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.75
• 重原子数：
  77.0
• 可旋转键数：
  24.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  267.17
• 氢给体数：
  0.0
• 氢受体数：
  23.0

反应信息

• 作为反应物：
  描述：

  methyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-β-D-glucopyranosyl-(1→4)-2,3,6-tri-O-benzyl-α-D-glucopyranose 在 sodium methylate 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 4.0h， 以79%的产率得到(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
  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：

  甲基2,3,6-三-O-苄基-ALPHA-D-吡喃葡萄糖苷 、 2,3,6,2',3',4',6'-hepta-O-acetyl-α-D-maltosyl bromide 在 silver trifluoromethanesulfonate 、 1,1,3,3-四甲基脲 作用下， 以 二氯甲烷 为溶剂， 以95%的产率得到methyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-β-D-glucopyranosyl-(1→4)-2,3,6-tri-O-benzyl-α-D-glucopyranose
  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

• Glycosylation Enabled by Successive Rhodium(II) and Brønsted Acid Catalysis
  作者：Lingkui Meng、Peng Wu、Jing Fang、Ying Xiao、Xiong Xiao、Guangsheng Tu、Xiang Ma、Shuang Teng、Jing Zeng、Qian Wan

  DOI：10.1021/jacs.9b04619

  日期：2019.7.31

  reaction comprises two chronological meticulously-designed catalytic cycles: 1) rhodium-catalyzed formation of sulfonium ylide; 2) Brønsted acid-catalyzed formation of sulfonium ion. This protocol highlight-ed an effective and robust tactic to prepare glycosyl sulfonium ion from glycosyl sulfonium ylide precursor amenable for glycosylation.

  在此，我们报道了一种高效的糖基化反应，包括两个按时间顺序精心设计的催化循环：1）铑催化形成锍叶立德；2) Brønsted 酸催化形成锍离子。该协议强调了一种有效且稳健的策略，可从适合糖基化的糖基锍叶立德前体制备糖基锍离子。