methyl 3-O-allyl-2,4,6-tri-O-benzoyl-β-D-glucopyranosyl-(1->3)-4,6-O-benzylidene-α-D-glucopyranoside | 802941-69-1

• 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-allyl-2,4,6-tri-O-benzoyl-β-D-glucopyranosyl-(1->3)-4,6-O-benzylidene-α-D-glucopyranoside
• CAS: 802941-69-1
• 化学式: C₄₄H₄₄O₁₄
• 分子量: 796.825
• InChiKey: PPJUGHYCDXASLY-DBARNPIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.82
• 重原子数：
  58.0
• 可旋转键数：
  14.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  163.74
• 氢给体数：
  1.0
• 氢受体数：
  14.0

反应信息

• 作为反应物：
  描述：

  methyl 3-O-allyl-2,4,6-tri-O-benzoyl-β-D-glucopyranosyl-(1->3)-4,6-O-benzylidene-α-D-glucopyranoside 在 palladium dichloride 作用下， 以 吡啶 、 甲醇 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 methyl 2,4,6-tri-O-benzoyl-β-D-glucopyranosyl-(1->3)-2-O-acetyl-4,6-O-benzylidene-α-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of an α-linked dimer of the trisaccharide repeating unit of the exopolysaccharide produced by Pediococcus damnosus 2.6

  摘要：

  A hexasaccharide, beta-D-Glcp-(1-->3)-[beta-D-Glcp-(1-->2)]-alpha-D-Glcp-(1-->3)-beta-D-Glcp-(1-->3)-[beta-D-Glcp-(1-->2)]-D-Glcp, the alpha-linked dimer of the trisaccharide repeating unit of the exopolysaccharide produced by Pediococcus damnosus 2.6, was synthesized as its methyl glycoside. Condensation of fully benzoylated alpha-D-glucopyranosyl trichloroacetimidate (1) with isopropyl 4,6-O-benzylid,ene-1-thio-beta-D-glucopyranoside (2) selectively furnished (1-->3)-linked disaccharide 3, and subsequent 2-O-acetylation, desulfation, and trichloroacetimidate formation afforded the disaccharide donor 6. Meanwhile, selective 3-O-coupling of methyl 4,6-O-benzylidene-alpha-D-glucopyranoside (8) with 3-O-allyl-2,4,6-tri-O-benzoyl-alpha-D-glucopyranosyl trichloroacetimidate (7), followed by coupling with 1 gave the trisaccharide 10. Removal of the benzylidene group of 10, benzoylation, and deallylation produced the trisaccharide acceptor 12. Condensation of 12 with 6 yielded a pentasaccharide mixture 13 with (3 and a isomers in a ratio of 2:1. Removal of the benzylidene group of 13, followed by benzoylation gave the pentasaccharide mixture 14. Selective 2"'-deacetylation of the isolated beta-linked 14 beta with MeCOCl/MeOH/CH2Cl2 did not give the expected pentasaccharide acceptor, and serious decomposition occurred, indicating a large steric hindrance at C-2"'. Alternatively, 2,3-di-O-glycosylation of allyl 4,6-O-benzylidene-beta-D-glucopyranoside (21) with 1 gave 22, then deallylation and trichloroacetimidate formation afforded the trisaccharide donor 24. Condensation of 12 with 24 furnished only the alpha-linked hexasaccharide 25, and its deprotection gave the free hexaoside 27. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2004.07.026
• 作为产物：
  描述：

  4,6-O-benzylidene-1-O-methyl-α-D-glucopyranoside 、 3-O-allyl-2,4,6-tri-O-benzoyl-α-D-glucopyranosyl trichloroacetimidate 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以57%的产率得到methyl 3-O-allyl-2,4,6-tri-O-benzoyl-β-D-glucopyranosyl-(1->3)-4,6-O-benzylidene-α-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of an α-linked dimer of the trisaccharide repeating unit of the exopolysaccharide produced by Pediococcus damnosus 2.6

  摘要：

  A hexasaccharide, beta-D-Glcp-(1-->3)-[beta-D-Glcp-(1-->2)]-alpha-D-Glcp-(1-->3)-beta-D-Glcp-(1-->3)-[beta-D-Glcp-(1-->2)]-D-Glcp, the alpha-linked dimer of the trisaccharide repeating unit of the exopolysaccharide produced by Pediococcus damnosus 2.6, was synthesized as its methyl glycoside. Condensation of fully benzoylated alpha-D-glucopyranosyl trichloroacetimidate (1) with isopropyl 4,6-O-benzylid,ene-1-thio-beta-D-glucopyranoside (2) selectively furnished (1-->3)-linked disaccharide 3, and subsequent 2-O-acetylation, desulfation, and trichloroacetimidate formation afforded the disaccharide donor 6. Meanwhile, selective 3-O-coupling of methyl 4,6-O-benzylidene-alpha-D-glucopyranoside (8) with 3-O-allyl-2,4,6-tri-O-benzoyl-alpha-D-glucopyranosyl trichloroacetimidate (7), followed by coupling with 1 gave the trisaccharide 10. Removal of the benzylidene group of 10, benzoylation, and deallylation produced the trisaccharide acceptor 12. Condensation of 12 with 6 yielded a pentasaccharide mixture 13 with (3 and a isomers in a ratio of 2:1. Removal of the benzylidene group of 13, followed by benzoylation gave the pentasaccharide mixture 14. Selective 2"'-deacetylation of the isolated beta-linked 14 beta with MeCOCl/MeOH/CH2Cl2 did not give the expected pentasaccharide acceptor, and serious decomposition occurred, indicating a large steric hindrance at C-2"'. Alternatively, 2,3-di-O-glycosylation of allyl 4,6-O-benzylidene-beta-D-glucopyranoside (21) with 1 gave 22, then deallylation and trichloroacetimidate formation afforded the trisaccharide donor 24. Condensation of 12 with 24 furnished only the alpha-linked hexasaccharide 25, and its deprotection gave the free hexaoside 27. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2004.07.026