(3aS,4R,6S,7R,7aR)-6-[(2R,3S,4R,5R,6R)-5-azido-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-4-hydroxy-6-methoxyoxan-3-yl]oxy-4-[[tert-butyl(diphenyl)silyl]oxymethyl]-2-methoxy-2-methyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-ol | 1055041-32-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3aS,4R,6S,7R,7aR)-6-[(2R,3S,4R,5R,6R)-5-azido-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-4-hydroxy-6-methoxyoxan-3-yl]oxy-4-[[tert-butyl(diphenyl)silyl]oxymethyl]-2-methoxy-2-methyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-ol
• CAS: 1055041-32-1
• 化学式: C₄₈H₆₃N₃O₁₁Si₂
• 分子量: 914.213
• InChiKey: CKXDHKQLJAXERB-MRUAFJJKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.13
• 重原子数：
  64
• 可旋转键数：
  17
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  138
• 氢给体数：
  2
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  (3aS,4R,6S,7R,7aR)-6-[(2R,3S,4R,5R,6R)-5-azido-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-4-hydroxy-6-methoxyoxan-3-yl]oxy-4-[[tert-butyl(diphenyl)silyl]oxymethyl]-2-methoxy-2-methyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-ol 在 吡啶 、 溶剂黄146 作用下， 以 甲苯 为溶剂， 反应 5.0h， 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
• 作为产物：
  描述：

  methyl O-β-D-galactopyranosyl-(1-4)-2-azido-2-deoxy-β-D-glucopyranoside 在 camphor-10-sulfonic acid 、 silver nitrate 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 0.5h， 生成 (3aS,4R,6S,7R,7aR)-6-[(2R,3S,4R,5R,6R)-5-azido-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-4-hydroxy-6-methoxyoxan-3-yl]oxy-4-[[tert-butyl(diphenyl)silyl]oxymethyl]-2-methoxy-2-methyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-ol
  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