methyl 2-azido-6-O-tert-butyldiphenylsilyl-4-O-(6-O-tert-butyldiphenylsilyl-β-D-galactopyranosyl)-2-deoxy-β-D-glucopyranoside | 937182-89-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-azido-6-O-tert-butyldiphenylsilyl-4-O-(6-O-tert-butyldiphenylsilyl-β-D-galactopyranosyl)-2-deoxy-β-D-glucopyranoside
• 英文别名: (2S,3R,4S,5R,6R)-2-[(2R,3S,4R,5R,6R)-5-azido-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-4-hydroxy-6-methoxyoxan-3-yl]oxy-6-[[tert-butyl(diphenyl)silyl]oxymethyl]oxane-3,4,5-triol
• CAS: 937182-89-3
• 化学式: C₄₅H₅₉N₃O₁₀Si₂
• 分子量: 858.149
• InChiKey: AVMYBIXMFKQDNW-SCWOTMKNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.74
• 重原子数：
  60
• 可旋转键数：
  16
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  151
• 氢给体数：
  4
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  methyl 2-azido-6-O-tert-butyldiphenylsilyl-4-O-(6-O-tert-butyldiphenylsilyl-β-D-galactopyranosyl)-2-deoxy-β-D-glucopyranoside 在 吡啶 、 camphor-10-sulfonic acid 作用下， 以 乙腈 为溶剂， 生成 [(2R,3S,4R,5R,6R)-3-[[(3aS,4R,6S,7R,7aS)-7-acetyloxy-4-[[tert-butyl(diphenyl)silyl]oxymethyl]-2-methoxy-2-methyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-6-yl]oxy]-5-azido-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-6-methoxyoxan-4-yl] acetate
  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 、 叔丁基二苯基氯硅烷 在 silver nitrate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 以32%的产率得到methyl 2-azido-6-O-tert-butyldiphenylsilyl-4-O-(3,6-di-O-tert-butyldiphenylsilyl-β-D-galactopyranosyl)-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