methyl 2,4,6-tri-O-benzoyl-β-D-mannopyranosyl-(1-4)-2,3,6-tri-O-benzoyl-α-D-glucopyranoside | 211617-01-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,4,6-tri-O-benzoyl-β-D-mannopyranosyl-(1-4)-2,3,6-tri-O-benzoyl-α-D-glucopyranoside
• CAS: 211617-01-5
• 化学式: C₅₅H₄₈O₁₇
• 分子量: 980.976
• InChiKey: WSJHDUXNOKJFRQ-ZHQYRSKDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.45
• 重原子数：
  72.0
• 可旋转键数：
  17.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  214.95
• 氢给体数：
  1.0
• 氢受体数：
  17.0

反应信息

• 作为反应物：
  描述：

  2,3,6,2',3',4',6'-hepta-O-acetyl-α-D-lactosyl trichloroacetimidate 、 methyl 2,4,6-tri-O-benzoyl-β-D-mannopyranosyl-(1-4)-2,3,6-tri-O-benzoyl-α-D-glucopyranoside 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 以70%的产率得到methyl (2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-(1-4)-2,3,6-tri-O-acetyl-β-D-glucopyranosyl-(1-3)-2,4,6-tri-O-benzoyl-β-D-mannopyranosyl-(1-4)-2,3,6-tri-O-benzoyl-α-D-glucopyranoside
  参考文献：
  名称：

  Glycosylation via locked anomeric configuration: stereospecific synthesis of oligosaccharides containing the β-d-mannopyranosyl and β-l-rhamnopyranosyl linkage11For a preliminary account of this work, see ref. [7].

  摘要：

  cis-1,2-Stannylene acetals of D-mannose and L-rhamnose, formed preferentially from the free sugars treated with dibutyltin oxide, are capable of displacing the trifluoromethanesulfonyl (triflyl) leaving groups in carbohydrates to give, with retention of configuration at the anomeric center in the nucleophile, cis-1,2-linked oligosaccharides. In the case of secondary triflates, the new glycosidic linkage is formed with complete inversion of configuration in the electrophile. Both the reactivity of the electrophile and nucleophilicity of oxygens in the stannylene complex affect the overall outcome of the reaction. From the comparison of results of a number of glycosylations via stannylene acetals, it appears that nucleophilicity of oxygens involved in the cis-1,2-acetals decreases in the order: equatorial anomeric > equatorial non-anomeric > axial anomeric. Consequently, treatment of the stannylene acetal prepared from D-mannose (mainly the cis-1,2-stannylene compound in admixture with a small proportion of the cis-2,3-stannylene acetal) with methyl 2,3,4-tri-O-benzoyl-6-O-trifluoromethanesulfonyl-alpha-D-glucopyranoside yielded, in addition to the expected beta-D-mannopyranoside (major), a product of non-anomeric alkylation at O-3. On the other hand, glycosylation of the stannylene acetal derived from maltose with methyl 2,3,6-tri-O-benzoyl-4-O-trifluoromethanesulfonyl-alpha-D-galactopyranoside gave almost exclusively a non-glycosidically, (2 --> 4)-linked pseudo-trisaccharide. Combination of the glycosylation via locked anomeric configuration with conventional glycosylations, to yield higher oligosaccharides, is also demonstrated. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(98)00057-3
• 作为产物：
  描述：

  methyl 2,4,6-tri-O-benzoyl-3-O-benzyl-β-D-mannopyranosyl-(1-4)-2,3,6-tri-O-benzoyl-α-D-glucopyranoside 在 氢气 作用下， 以 乙醇 为溶剂， 反应 48.0h， 以82.4%的产率得到methyl 2,4,6-tri-O-benzoyl-β-D-mannopyranosyl-(1-4)-2,3,6-tri-O-benzoyl-α-D-glucopyranoside
  参考文献：
  名称：

  Glycosylation via locked anomeric configuration: stereospecific synthesis of oligosaccharides containing the β-d-mannopyranosyl and β-l-rhamnopyranosyl linkage11For a preliminary account of this work, see ref. [7].

  摘要：

  cis-1,2-Stannylene acetals of D-mannose and L-rhamnose, formed preferentially from the free sugars treated with dibutyltin oxide, are capable of displacing the trifluoromethanesulfonyl (triflyl) leaving groups in carbohydrates to give, with retention of configuration at the anomeric center in the nucleophile, cis-1,2-linked oligosaccharides. In the case of secondary triflates, the new glycosidic linkage is formed with complete inversion of configuration in the electrophile. Both the reactivity of the electrophile and nucleophilicity of oxygens in the stannylene complex affect the overall outcome of the reaction. From the comparison of results of a number of glycosylations via stannylene acetals, it appears that nucleophilicity of oxygens involved in the cis-1,2-acetals decreases in the order: equatorial anomeric > equatorial non-anomeric > axial anomeric. Consequently, treatment of the stannylene acetal prepared from D-mannose (mainly the cis-1,2-stannylene compound in admixture with a small proportion of the cis-2,3-stannylene acetal) with methyl 2,3,4-tri-O-benzoyl-6-O-trifluoromethanesulfonyl-alpha-D-glucopyranoside yielded, in addition to the expected beta-D-mannopyranoside (major), a product of non-anomeric alkylation at O-3. On the other hand, glycosylation of the stannylene acetal derived from maltose with methyl 2,3,6-tri-O-benzoyl-4-O-trifluoromethanesulfonyl-alpha-D-galactopyranoside gave almost exclusively a non-glycosidically, (2 --> 4)-linked pseudo-trisaccharide. Combination of the glycosylation via locked anomeric configuration with conventional glycosylations, to yield higher oligosaccharides, is also demonstrated. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(98)00057-3