p-methoxyphenyl 3-O-allyl-4,6-O-benzylidene-2-O-benzoyl-α-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzoyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzoyl-β-D-glucopyranoside | 578007-61-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: p-methoxyphenyl 3-O-allyl-4,6-O-benzylidene-2-O-benzoyl-α-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzoyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzoyl-β-D-glucopyranoside
• CAS: 578007-61-1
• 化学式: C₈₄H₇₄O₂₄
• 分子量: 1467.5
• InChiKey: XRRMGVGUGLFRFO-WCEDLZBHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.55
• 重原子数：
  108.0
• 可旋转键数：
  27.0
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  276.4
• 氢给体数：
  0.0
• 氢受体数：
  24.0

反应信息

• 作为反应物：
  描述：

  p-methoxyphenyl 3-O-allyl-4,6-O-benzylidene-2-O-benzoyl-α-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzoyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzoyl-β-D-glucopyranoside 在 溶剂黄146 作用下， 反应 2.0h， 以91%的产率得到p-methoxyphenyl 3-O-allyl-2-O-benzoyl-α-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzoyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzoyl-β-D-glucopyranoside
  参考文献：
  名称：

  A concise and practical synthesis of antigenic globotriose, α-d-Gal-(1→4)-β-d-Gal-(1→4)-β-d-Glc

  摘要：

  A concise and practical synthesis of the antigenic globotriose, alpha-D-Gal-(1 -> 4)-beta-D-Gal-(1 -> 4)-beta-D-Glc (13), was achieved by coupling of a monosaccharide donor, 3-O-allyl-2-O-benzoyl-4,6-O-benzylidene-alpha-D-galactopyranosyl trichloroacetimidate (4) with a disaccharide acceptor, p-methoxyphenyl 2,3,6-tri-O-benzoyl-beta-D-galactopyranosyl-(1 -> 4)-2,3,6-tri-O-benzoyl-beta-D-glucopyranoside (8), followed by deprotection. In spite of the existence of a C-2-ester substituent capable of neighboring-group participation in the donor, the coupling gave exclusively the alpha-linkage in satisfactory yield. The acceptor 8 was readily obtained from selective 3-O-benzoylation of the galactosyl. ring of p-methoxyphenyl 2,6-di-O-benzoyl-beta-D-galactopyranosyl-(1 -> 4)-2,3,6-tri-O-benzoyl-beta-D-glucopyranoside (7), which was prepared from p-methoxyphenyl beta-D-lactoside (5) via isopropylidenation, benzoylation, and deisopropylidenation. Donor 4 was obtained from p-methoxylphenyl 3-O-allyl-2,4,6-tri-O-benzoyl-beta-D-galactopyranoside (1) via selective 4,6-di-O-debenzoylation, oxidative removal of 1-O-MP, benzylidenation, and trichloroacetimidate formation. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2006.03.029
• 作为产物：
  描述：

  3-O-allyl-2-O-benzoyl-4,6-O-benzylidene-α-D-galactopyranosyl trichloroacetimidate 、 p-methoxyphenyl 2,3,6-tri-O-benzoyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzoyl-β-D-glucopyranoside 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以89%的产率得到p-methoxyphenyl 3-O-allyl-4,6-O-benzylidene-2-O-benzoyl-α-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzoyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzoyl-β-D-glucopyranoside
  参考文献：
  名称：

  A concise and practical synthesis of antigenic globotriose, α-d-Gal-(1→4)-β-d-Gal-(1→4)-β-d-Glc

  摘要：

  A concise and practical synthesis of the antigenic globotriose, alpha-D-Gal-(1 -> 4)-beta-D-Gal-(1 -> 4)-beta-D-Glc (13), was achieved by coupling of a monosaccharide donor, 3-O-allyl-2-O-benzoyl-4,6-O-benzylidene-alpha-D-galactopyranosyl trichloroacetimidate (4) with a disaccharide acceptor, p-methoxyphenyl 2,3,6-tri-O-benzoyl-beta-D-galactopyranosyl-(1 -> 4)-2,3,6-tri-O-benzoyl-beta-D-glucopyranoside (8), followed by deprotection. In spite of the existence of a C-2-ester substituent capable of neighboring-group participation in the donor, the coupling gave exclusively the alpha-linkage in satisfactory yield. The acceptor 8 was readily obtained from selective 3-O-benzoylation of the galactosyl. ring of p-methoxyphenyl 2,6-di-O-benzoyl-beta-D-galactopyranosyl-(1 -> 4)-2,3,6-tri-O-benzoyl-beta-D-glucopyranoside (7), which was prepared from p-methoxyphenyl beta-D-lactoside (5) via isopropylidenation, benzoylation, and deisopropylidenation. Donor 4 was obtained from p-methoxylphenyl 3-O-allyl-2,4,6-tri-O-benzoyl-beta-D-galactopyranoside (1) via selective 4,6-di-O-debenzoylation, oxidative removal of 1-O-MP, benzylidenation, and trichloroacetimidate formation. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2006.03.029

文献信息

• Unusual α-glycosylation with galactosyl donors with a C2 ester capable of neighboring group participation
  作者：Langqiu Chen、Fanzuo Kong

  DOI：10.1016/s0040-4039(03)00673-7

  日期：2003.4

  6-O-benzylidene-1-thio-β-d-galactopyranoside (15) as the donor, glycosylation of 2 gave α-linked products only, indicating that 4,6-O-benzylidenation led to α-stereoselectivity in spite of the C2 ester capable of neighboring group participation. Using 15 as the donor, glycosylation of mannose derivatives with 2- or 3-OH's, glucose with 2- or 3-OH's, galactose with 2-, or 3-, or 4-OH's, glucosamine and glucuronic

  4-甲氧基苯基2,3,6-三-O-苯甲酰基-β-d-吡喃葡萄糖苷（2）与异丙基3 - O-烯丙基-2,4,6-三-O-苯甲酰基-（9）或6的糖基化- ø -烯丙基-2,3,4-三ö苯甲酰基-1-硫代β-d吡喃半乳糖苷（7）作为供体，得到的α-和β连接混合物，而用异丙3- ö -氯乙酰基-2- ø -苯甲酰基-4,6- ö -benzylidene-（13）和异丙基3- ö -烯丙基-2- ø -苯甲酰基-4,6- ø -亚苄基-1-硫代-β-β-d吡喃半乳糖苷（15）作为供体，2的糖基化仅产生α-连接的产物，表明尽管C2酯能够相邻基团参与，但4,6- O-亚苄基化仍导致α-立体选择性。使用15作为供体，甘露糖衍生物与2-或3-OH's进行糖基化，葡萄糖与2-或3-OH's进行葡萄糖基化，半乳糖与2-或3-或4-或4-OH's进行半乳糖苷，葡糖胺和葡萄糖醛酸与4-OH进行糖基化。 ，以及带有