methyl 3-O-acetyl-2-azido-4-O-(2,4-di-O-acetyl-6-O-tert-butyldiphenylsilyl-β-D-galactopyranosyl)-6-O-tert-butyldiphenylsilyl-2-deoxy-β-D-glucopyranoside | 937182-92-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl 3-O-acetyl-2-azido-4-O-(2,4-di-O-acetyl-6-O-tert-butyldiphenylsilyl-β-D-galactopyranosyl)-6-O-tert-butyldiphenylsilyl-2-deoxy-β-D-glucopyranoside
• 英文别名: [(2R,3R,4S,5R,6S)-5-acetyloxy-6-[(2R,3S,4R,5R,6R)-4-acetyloxy-5-azido-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-6-methoxyoxan-3-yl]oxy-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-4-hydroxyoxan-3-yl] acetate
• CAS: 937182-92-8
• 化学式: C₅₁H₆₅N₃O₁₃Si₂
• 分子量: 984.26
• InChiKey: XCUKJACMUNKOKC-DOUNFTBZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.46
• 重原子数：
  69
• 可旋转键数：
  22
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  169
• 氢给体数：
  1
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  methyl 3-O-acetyl-2-azido-4-O-(2,4-di-O-acetyl-6-O-tert-butyldiphenylsilyl-β-D-galactopyranosyl)-6-O-tert-butyldiphenylsilyl-2-deoxy-β-D-glucopyranoside 、 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl-O-trichloroacetimidate 在 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 以44%的产率得到methyl 3-O-acetyl-4-O-[2,4-di-O-acetyl-6-O-tert-butyldiphenylsilyl-3-O-(3,4,6-tri-O-acetyl-2-deoxy-2-N-phthalimido-β-D-glucopyranosyl)-β-D-galactopyranosyl]-2-azido-6-O-tert-butyldiphenylsilyl-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  Selective Protection of 2-Azido-lactose and in Situ Ferrier Rearrangement during Glycosylation:  Synthesis of a Dimeric Lewis X Fragment

  摘要：

  In our efforts to design new anti-cancer vaccines based on the tumor associated carbohydrate antigen dimeric Le(x), we have synthesized the fragment GlcNAc-beta-(1 -> 3)-Gal-beta-(1 -> 4)-GlcNAc-beta-(1 -> O)-Me. Although it is notoriously difficult to chemically protect the primary OH groups in beta-lactoside derivatives, a 6,6'-disilylated intermediate was prepared in 82% yield. It was converted to a glycosyl acceptor free at O-3' that was glycosylated with a 2-deoxy-2-phthalimido trichloroacetimidate glucosyl donor. This glycosylation required large amounts of TMSOTf to proceed. Such conditions led to the formation of a Ferrier rearrangement glycosylation product. Despite these hurdles, the desired trisaccharide was isolated in 53% yield and easily deprotected in four steps.

  DOI：

  10.1021/jo062541y
• 作为产物：
  描述：

  methyl O-β-D-galactopyranosyl-(1-4)-2-azido-2-deoxy-β-D-glucopyranoside 在 吡啶 、 camphor-10-sulfonic acid 、 silver nitrate 、 溶剂黄146 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 反应 5.5h， 生成 methyl 3-O-acetyl-2-azido-4-O-(2,4-di-O-acetyl-6-O-tert-butyldiphenylsilyl-β-D-galactopyranosyl)-6-O-tert-butyldiphenylsilyl-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  Selective Protection of 2-Azido-lactose and in Situ Ferrier Rearrangement during Glycosylation:  Synthesis of a Dimeric Lewis X Fragment

  摘要：

  In our efforts to design new anti-cancer vaccines based on the tumor associated carbohydrate antigen dimeric Le(x), we have synthesized the fragment GlcNAc-beta-(1 -> 3)-Gal-beta-(1 -> 4)-GlcNAc-beta-(1 -> O)-Me. Although it is notoriously difficult to chemically protect the primary OH groups in beta-lactoside derivatives, a 6,6'-disilylated intermediate was prepared in 82% yield. It was converted to a glycosyl acceptor free at O-3' that was glycosylated with a 2-deoxy-2-phthalimido trichloroacetimidate glucosyl donor. This glycosylation required large amounts of TMSOTf to proceed. Such conditions led to the formation of a Ferrier rearrangement glycosylation product. Despite these hurdles, the desired trisaccharide was isolated in 53% yield and easily deprotected in four steps.

  DOI：

  10.1021/jo062541y