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 | 937182-93-9

• 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-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
• 英文别名: [(2R,3S,4R,5R,6S)-3,4-diacetyloxy-6-[(2S,3R,4S,5S,6R)-3,5-diacetyloxy-2-[(2R,3S,4R,5R,6R)-4-acetyloxy-5-azido-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-6-methoxyoxan-3-yl]oxy-6-[[tert-butyl(diphenyl)silyl]oxymethyl]oxan-4-yl]oxy-5-(1,3-dioxoisoindol-2-yl)oxan-2-yl]methyl acetate
• CAS: 937182-93-9
• 化学式: C₇₁H₈₄N₄O₂₂Si₂
• 分子量: 1401.63
• InChiKey: MDEKLTLWQKTGHR-VFCWVWDWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  99
• 可旋转键数：
  32
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  283
• 氢给体数：
  0
• 氢受体数：
  24

反应信息

• 作为反应物：
  描述：

  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 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 生成
  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 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