methyl 3-O-benzyl-β-D-mannopyranosyl-(1-6)-2,3,4-tri-O-benzoyl-α-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3-O-benzyl-β-D-mannopyranosyl-(1-6)-2,3,4-tri-O-benzoyl-α-D-glucopyranoside
• 英文别名: Bn(-3)Man(b1-6)[Bz(-2)][Bz(-3)][Bz(-4)]a-Glc1Me；[(2R,3R,4S,5R,6S)-4,5-dibenzoyloxy-2-[[(2R,3S,4S,5R,6R)-3,5-dihydroxy-6-(hydroxymethyl)-4-phenylmethoxyoxan-2-yl]oxymethyl]-6-methoxyoxan-3-yl] benzoate
• 化学式: C₄₁H₄₂O₁₄
• 分子量: 758.776
• InChiKey: GUZNYLJSDWTULU-NQVGDSCBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  55
• 可旋转键数：
  17
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  186
• 氢给体数：
  3
• 氢受体数：
  14

反应信息

• 作为产物：
  描述：

  甲基-D-丙噻 在 4 A molecular sieve 、 硫酸 、 四丁基氟化铵 、 二正丁基氧化锡 、 cesium fluoride 作用下， 以 溶剂黄146 为溶剂， 反应 48.58h， 生成 methyl 3-O-benzyl-β-D-mannopyranosyl-(1-6)-2,3,4-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

文献信息

• A Fundamentally New, Simple, Stereospecific Synthesis of Oligosaccharides Containing the β-Mannopyranosyl and β-Rhamnopyranosyl Linkage
  作者：György Hodosi、Pavol Kováč

  DOI：10.1021/ja964021y

  日期：1997.3.1

  oligosaccharides in biological processes1 has been recognized for a long time. Consequently, synthetic oligosaccharides have become indispensable probes for the life sciences.2 Methods for the chemical synthesis of oligosaccharides are based on a two-step process: The first comprises activation of the anomeric center to generate a glycosyl donor, and the second is its transfer to a glycosyl acceptor. The

  长期以来，人们已经认识到寡糖在生物过程中的重要作用 1。因此，合成寡糖已成为生命科学不可或缺的探针。 2 寡糖的化学合成方法基于两步过程：第一步包括激活异头中心以产生糖基供体，第二步是其转移到糖基受体。反应的立体化学结果取决于复杂的立体电子效应以及糖基供体中 O-2 处的基团的存在与否，能够相邻基团参与。 3 除了极少数情况，当糖基供体和糖基偶联时受体几乎完全是 SN2 过程，4 糖基供体的反应涉及氧碳鎓离子的形成 (1)。因此，
• 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].
  作者：György Hodosi、Pavol Kovác̆

  DOI：10.1016/s0008-6215(98)00057-3

  日期：1998.3

  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.