Methyl 2-acetamido-4,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside | 139760-22-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 2-acetamido-4,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside
• 英文别名: N-[(2S,3R,4R,5S,6R)-4-hydroxy-2-methoxy-5-phenylmethoxy-6-(phenylmethoxymethyl)oxan-3-yl]acetamide
• CAS: 139760-22-8
• 化学式: C₂₃H₂₉NO₆
• 分子量: 415.486
• InChiKey: LUORVYLCGRAXGT-JLMDMGSGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  86.2
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Methyl 2-acetamido-4,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside 在 palladium on activated charcoal 2,4,6-三甲基吡啶 、 氢气 、 sodium methylate 、 silver perchlorate 作用下， 以 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 25.0~50.0 ℃ 、101.33 kPa 条件下， 反应 20.0h， 生成 Methyl O-α-L-rhamnopyranosyl-(1->2)-O-α-D-galactopyranosyl-(1->3)-2-acetamido-2-deoxy-α-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of ligands related to the O-specific antigen of type 1 Shigella dysenteriae. 3. Glycosylation of 4,6-O-substituted derivatives of methyl 2-acetamido-2-deoxy-.alpha.-D-glucopyranoside with glycosyl donors derived from mono- and oligosaccharides.

  摘要：

  Methyl O-(2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl)-(1 --> 3)-2,4-di-O-benzoyl-alpha-L-rhamnopyranoside, obtained by silver trifluoromethanesulfonate-mediated condensation of methyl 2,4-di-O-benzoyl-alpha-L-rhamnopyranoside and 2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl bromide (3), was cleaved with dichloromethyl methyl ether (DCMME) to give O-(2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl)-(1 --> 3)-2,4-di-O-benzoyl-alpha-L-rhamnopyranosyl chloride (9). Condensations of 1,3,4,6-tetra-O-acetyl-alpha-D-galactopyranose with 3 and 9, followed by treatment of the products with DCMME yielded, respectively, glycosyl chlorides 12 and 17. Each of these, as well as 2,3,4,6-tetra-O-benzyl-alpha-D-galactopyranosyl chloride was condensed with 4,6-O-substituted (benzylidene, tetraisopropyl-disiloxane-1,3-diyl, or benzyl) derivatives of methyl 2-acetamido-2-deoxy-alpha-D-glucopyranoside, using CH2Cl2, ether, or a mixture thereof as the solvent. The formation of the desired alpha-D-galactopyranosyl linkage was favored when ether was the solvent. Under these conditions, however, the combined yield of the condensation products decreased, especially when less reactive synthons were used. The alpha-linked products obtained were deprotected to give the methyl alpha-glycosides of the tetra, tri-, and the disaccharide related to the chemical repeating unit of the O-specific side chain of the lipopolysaccharide of Shigella dysenteriae type 1. Synthesis of methyl alpha-glycosides of three other constituents of the same polymeric antigen [alpha-L-Rha-(1 --> 3)-alpha-L-Rha, alpha-L-Rha-(1 --> 2)-alpha-D-Gal, and alpha-L-Rha-(1 --> 3)-alpha-L-Rha-(1 --> 2)-alpha-D-Gal] are also described.

  DOI：

  10.1021/jo00034a047
• 作为产物：
  描述：

  methyl 2-acetamido-3-O-acetyl-4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside 在 氢氧化钾 、 ammonium cerium(IV) nitrate 、 Amberlite IRA 400 (OH^--form) 、 碘 作用下， 以 甲醇 、 水 、 二甲基亚砜 、 乙腈 为溶剂， 反应 15.33h， 生成 Methyl 2-acetamido-4,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of ligands related to the O-specific antigen of type 1 Shigella dysenteriae. 3. Glycosylation of 4,6-O-substituted derivatives of methyl 2-acetamido-2-deoxy-.alpha.-D-glucopyranoside with glycosyl donors derived from mono- and oligosaccharides.

  摘要：

  Methyl O-(2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl)-(1 --> 3)-2,4-di-O-benzoyl-alpha-L-rhamnopyranoside, obtained by silver trifluoromethanesulfonate-mediated condensation of methyl 2,4-di-O-benzoyl-alpha-L-rhamnopyranoside and 2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl bromide (3), was cleaved with dichloromethyl methyl ether (DCMME) to give O-(2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl)-(1 --> 3)-2,4-di-O-benzoyl-alpha-L-rhamnopyranosyl chloride (9). Condensations of 1,3,4,6-tetra-O-acetyl-alpha-D-galactopyranose with 3 and 9, followed by treatment of the products with DCMME yielded, respectively, glycosyl chlorides 12 and 17. Each of these, as well as 2,3,4,6-tetra-O-benzyl-alpha-D-galactopyranosyl chloride was condensed with 4,6-O-substituted (benzylidene, tetraisopropyl-disiloxane-1,3-diyl, or benzyl) derivatives of methyl 2-acetamido-2-deoxy-alpha-D-glucopyranoside, using CH2Cl2, ether, or a mixture thereof as the solvent. The formation of the desired alpha-D-galactopyranosyl linkage was favored when ether was the solvent. Under these conditions, however, the combined yield of the condensation products decreased, especially when less reactive synthons were used. The alpha-linked products obtained were deprotected to give the methyl alpha-glycosides of the tetra, tri-, and the disaccharide related to the chemical repeating unit of the O-specific side chain of the lipopolysaccharide of Shigella dysenteriae type 1. Synthesis of methyl alpha-glycosides of three other constituents of the same polymeric antigen [alpha-L-Rha-(1 --> 3)-alpha-L-Rha, alpha-L-Rha-(1 --> 2)-alpha-D-Gal, and alpha-L-Rha-(1 --> 3)-alpha-L-Rha-(1 --> 2)-alpha-D-Gal] are also described.

  DOI：

  10.1021/jo00034a047

文献信息

• Synthesis of ligands related to the O-specific antigen of type 1 Shigella dysenteriae. 3. Glycosylation of 4,6-O-substituted derivatives of methyl 2-acetamido-2-deoxy-.alpha.-D-glucopyranoside with glycosyl donors derived from mono- and oligosaccharides.
  作者：Pavol Kovac、Kevin J. Edgar

  DOI：10.1021/jo00034a047

  日期：1992.4

  Methyl O-(2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl)-(1 --> 3)-2,4-di-O-benzoyl-alpha-L-rhamnopyranoside, obtained by silver trifluoromethanesulfonate-mediated condensation of methyl 2,4-di-O-benzoyl-alpha-L-rhamnopyranoside and 2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl bromide (3), was cleaved with dichloromethyl methyl ether (DCMME) to give O-(2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl)-(1 --> 3)-2,4-di-O-benzoyl-alpha-L-rhamnopyranosyl chloride (9). Condensations of 1,3,4,6-tetra-O-acetyl-alpha-D-galactopyranose with 3 and 9, followed by treatment of the products with DCMME yielded, respectively, glycosyl chlorides 12 and 17. Each of these, as well as 2,3,4,6-tetra-O-benzyl-alpha-D-galactopyranosyl chloride was condensed with 4,6-O-substituted (benzylidene, tetraisopropyl-disiloxane-1,3-diyl, or benzyl) derivatives of methyl 2-acetamido-2-deoxy-alpha-D-glucopyranoside, using CH2Cl2, ether, or a mixture thereof as the solvent. The formation of the desired alpha-D-galactopyranosyl linkage was favored when ether was the solvent. Under these conditions, however, the combined yield of the condensation products decreased, especially when less reactive synthons were used. The alpha-linked products obtained were deprotected to give the methyl alpha-glycosides of the tetra, tri-, and the disaccharide related to the chemical repeating unit of the O-specific side chain of the lipopolysaccharide of Shigella dysenteriae type 1. Synthesis of methyl alpha-glycosides of three other constituents of the same polymeric antigen [alpha-L-Rha-(1 --> 3)-alpha-L-Rha, alpha-L-Rha-(1 --> 2)-alpha-D-Gal, and alpha-L-Rha-(1 --> 3)-alpha-L-Rha-(1 --> 2)-alpha-D-Gal] are also described.