methyl O-(3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-glucopyranosyl)-(1-3)-O-(2,4-di-O-benzoyl-α-L-rhamnopyranosyl)-(1-3)-2,4-di-O-benzoyl-α-L-rhamnopyranoside | 142967-80-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl O-(3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-glucopyranosyl)-(1-3)-O-(2,4-di-O-benzoyl-α-L-rhamnopyranosyl)-(1-3)-2,4-di-O-benzoyl-α-L-rhamnopyranoside
• CAS: 142967-80-4
• 化学式: C₅₃H₅₅N₃O₂₀
• 分子量: 1054.03
• InChiKey: KPDLTPPMMXAQCN-ZSEXFFQASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.63
• 重原子数：
  76.0
• 可旋转键数：
  18.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  288.24
• 氢给体数：
  0.0
• 氢受体数：
  21.0

反应信息

• 作为反应物：
  描述：

  methyl O-(3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-glucopyranosyl)-(1-3)-O-(2,4-di-O-benzoyl-α-L-rhamnopyranosyl)-(1-3)-2,4-di-O-benzoyl-α-L-rhamnopyranoside 在 palladium on activated charcoal 氢气 、 sodium methylate 作用下， 以 甲醇 为溶剂， 生成 methyl O-(2-acetamido-2-deoxy-α-D-glucopyranosyl)-(1-3)-O-(α-L-rhamnopyranosyl)-(1-3)-α-L-rhamnopyranoside
  参考文献：
  名称：

  Stereoselective syntheses of a di-, tri-, and tetra-saccharide fragment of shigella dysenteriae type 1 O-antigen using 3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-d-glucopyranosyl chloride as a glycosyl donor

  摘要：

  Methyl 2,4-di-O-benzoyl-alpha-L-rhamnopyranoside (1) furnished a crystalline 3-0-bromoacetyl derivative that was treated with the dichloromethyl methyl ether-ZnCl2 reagent to give 2,4-di-O-benzoyl-3-O-bromoacetyl-alpha-L-rhamnopyranosyl chloride (3). Compounds 1 and 3 were condensed under the conditions of base-deficient, silver trifluoromethanesulfonate-mediated glycosylation to give a fully protected rhamnobioside, which on O-debromoacetylation afforded the disaccharide nucleophile 10. Similar condensation of 3 with methyl 3-O-benzoyl-4,6-O-benzylidene-alpha-D-galactopyranoside, followed by O-debromoacetylation and condensation of the thus formed methyl O-(2,4-di-O-benzoyl-alpha-L-rhamopyranosyl)-(1 --> 2)-4,6-O-benzylidene-3-O-benzoyl-alpha-D-galactopyranoside again with 3, gave the trisaccharide glycoside. Subsequent O-debromoacetylation gave 17, having only HO-3(3) unsubstituted. Silver perchlorate-mediated glycosylations of 1, 10, and 17 with 3.4.6-tri-O-acetyl-2-azido-2-deoxy-alpha-D-glucopyranosyl chloride afforded, with high alpha stereoselectivity, protected di-, tri-, and tetra-saccharide glycosides. Subsequent hydrogenation, followed by N-acetylation and O-deacylation, afforded three oligosaccharide glycosides having nonreducing terminal 2-acetamido-2-deoxy-alpha-D-glucopyranosyl residues and comprising successively larger portions of the repeating unit of Shigella dysenteriae type 1 O-antigen.

  DOI：

  10.1016/s0008-6215(00)90483-x
• 作为产物：
  描述：

  methyl O-(2,4-di-O-benzoyl-3-O-bromoacetyl-α-L-rhamnopyranosyl)-(1->3)-2,4-di-O-benzoyl-α-L-rhamnopyranoside 在 2,4,6-三甲基吡啶 、 silver perchlorate 、 硫脲 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 1.5h， 生成 methyl O-(3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-glucopyranosyl)-(1-3)-O-(2,4-di-O-benzoyl-α-L-rhamnopyranosyl)-(1-3)-2,4-di-O-benzoyl-α-L-rhamnopyranoside
  参考文献：
  名称：

  Stereoselective syntheses of a di-, tri-, and tetra-saccharide fragment of shigella dysenteriae type 1 O-antigen using 3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-d-glucopyranosyl chloride as a glycosyl donor

  摘要：

  Methyl 2,4-di-O-benzoyl-alpha-L-rhamnopyranoside (1) furnished a crystalline 3-0-bromoacetyl derivative that was treated with the dichloromethyl methyl ether-ZnCl2 reagent to give 2,4-di-O-benzoyl-3-O-bromoacetyl-alpha-L-rhamnopyranosyl chloride (3). Compounds 1 and 3 were condensed under the conditions of base-deficient, silver trifluoromethanesulfonate-mediated glycosylation to give a fully protected rhamnobioside, which on O-debromoacetylation afforded the disaccharide nucleophile 10. Similar condensation of 3 with methyl 3-O-benzoyl-4,6-O-benzylidene-alpha-D-galactopyranoside, followed by O-debromoacetylation and condensation of the thus formed methyl O-(2,4-di-O-benzoyl-alpha-L-rhamopyranosyl)-(1 --> 2)-4,6-O-benzylidene-3-O-benzoyl-alpha-D-galactopyranoside again with 3, gave the trisaccharide glycoside. Subsequent O-debromoacetylation gave 17, having only HO-3(3) unsubstituted. Silver perchlorate-mediated glycosylations of 1, 10, and 17 with 3.4.6-tri-O-acetyl-2-azido-2-deoxy-alpha-D-glucopyranosyl chloride afforded, with high alpha stereoselectivity, protected di-, tri-, and tetra-saccharide glycosides. Subsequent hydrogenation, followed by N-acetylation and O-deacylation, afforded three oligosaccharide glycosides having nonreducing terminal 2-acetamido-2-deoxy-alpha-D-glucopyranosyl residues and comprising successively larger portions of the repeating unit of Shigella dysenteriae type 1 O-antigen.

  DOI：

  10.1016/s0008-6215(00)90483-x