methyl 2,3-di-O-acetyl-6-O-benzyl-β-D-glucopyranoside | 162284-49-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3-di-O-acetyl-6-O-benzyl-β-D-glucopyranoside
• 英文别名: [(2R,3R,4S,5R,6R)-3-acetyloxy-5-hydroxy-2-methoxy-6-(phenylmethoxymethyl)oxan-4-yl] acetate
• CAS: 162284-49-3
• 化学式: C₁₈H₂₄O₈
• 分子量: 368.384
• InChiKey: RXVXPDCGHDLLIM-UYTYNIKBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  101
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl 2,3-di-O-acetyl-6-O-benzyl-β-D-glucopyranoside 在 2,4,6-三甲基吡啶 、 silver trifluoromethanesulfonate 、 三氯化铁 、 对甲苯磺酸 作用下， 以 吡啶 、 甲醇 、 硝基甲烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 1.25h， 生成 methyl 4-O-(2,3,4,6-tetrakis-O-(p-bromobenzoyl)-β-D-glucopyranosyl)-β-D-glucopyranoside
  参考文献：
  名称：

  Hydroxymethyl Rotamer Populations in Disaccharides

  摘要：

  Sixteen methyl glucopyranosyl glucopyranoside disaccharides (methyl beta-D-Glcp(p-Br-Bz)-(1-->alpha)-beta/alpha-D-Glcp) containing beta-glycosidic linkages (1-->2, 1-->3, 1-->4, and 1-->6) were synthesized and analyzed by means of CD and NMR spectroscopy in three different solvents. For each of these four types of disaccharides, a correlation was observed between the hydroxymethyl rotational populations around the C5-C6 bond of the glucopyranosyl residue II with the substituents and the anomeric configuration of the methoxyl group in residue I, as well as with the solvent. Nonbonded interactions, the stereoelectronic exo-anomeric effect, and hydrogen bonding were found to be responsible for the observed rotameric differences. Whereas the rotational populations of the (1-->6)-linked disaccharides are mainly dependent on the exo-anomeric effect, the (1-->2)-bonded disaccharides are strongly dependent on the anomeric configuration at C1, and the (1-->3)- and (1-->4)-linked disaccharides are mainly dependent on the substituents and the solvent. The population of the gt rotamer decreases as nonbonded interactions increase but increases as the exo-anomeric effect becomes greater, as well as in the presence of intramolecular hydrogen bonding to the endocyclic oxygen O5'. Comparison of the hydroxymethyl rotational preferences between our model disaccharides revealed a dependence on the glycosidic linkage type. Thus the population of the gg and gt rotamers decreases/increases from (1-->2)-(beta series), to (1-->6)-, to (1-->2)-(alpha series), to (1-->4)-, and to (1-->3)-bonded disaccharides respectively, while the tg rotamer population remains almost constant (around 20%), except for the (1-->3)- and (1-->4)-linked disaccharides with the intramolecular hydrogen bonding to O5', where this population decreases to 10%.

  DOI：

  10.1021/jo026913o
• 作为产物：
  描述：

  甲基 Β-D-吡喃葡萄糖苷 在 sodium cyanoborohydride 、 对甲苯磺酸 、 三氟乙酸 作用下， 以 四氢呋喃 、 吡啶 、 N,N-二甲基甲酰胺 为溶剂， 反应 336002.0h， 生成 methyl 2,3-di-O-acetyl-6-O-benzyl-β-D-glucopyranoside
  参考文献：
  名称：

  Hydroxymethyl Rotamer Populations in Disaccharides

  摘要：

  Sixteen methyl glucopyranosyl glucopyranoside disaccharides (methyl beta-D-Glcp(p-Br-Bz)-(1-->alpha)-beta/alpha-D-Glcp) containing beta-glycosidic linkages (1-->2, 1-->3, 1-->4, and 1-->6) were synthesized and analyzed by means of CD and NMR spectroscopy in three different solvents. For each of these four types of disaccharides, a correlation was observed between the hydroxymethyl rotational populations around the C5-C6 bond of the glucopyranosyl residue II with the substituents and the anomeric configuration of the methoxyl group in residue I, as well as with the solvent. Nonbonded interactions, the stereoelectronic exo-anomeric effect, and hydrogen bonding were found to be responsible for the observed rotameric differences. Whereas the rotational populations of the (1-->6)-linked disaccharides are mainly dependent on the exo-anomeric effect, the (1-->2)-bonded disaccharides are strongly dependent on the anomeric configuration at C1, and the (1-->3)- and (1-->4)-linked disaccharides are mainly dependent on the substituents and the solvent. The population of the gt rotamer decreases as nonbonded interactions increase but increases as the exo-anomeric effect becomes greater, as well as in the presence of intramolecular hydrogen bonding to the endocyclic oxygen O5'. Comparison of the hydroxymethyl rotational preferences between our model disaccharides revealed a dependence on the glycosidic linkage type. Thus the population of the gg and gt rotamers decreases/increases from (1-->2)-(beta series), to (1-->6)-, to (1-->2)-(alpha series), to (1-->4)-, and to (1-->3)-bonded disaccharides respectively, while the tg rotamer population remains almost constant (around 20%), except for the (1-->3)- and (1-->4)-linked disaccharides with the intramolecular hydrogen bonding to O5', where this population decreases to 10%.

  DOI：

  10.1021/jo026913o

文献信息

• Synthesis of new sulfated disaccharides for the modulation of TLR4-dependent inflammation
  作者：Rachid Naïtaleb、Agnès Denys、Fabrice Allain、Jérôme Ausseil、Sylvestre Toumieux、José Kovensky

  DOI：10.1039/d1ob00692d

  日期：——

  the BBB. A suitable protected donor and acceptor, obtained from a unique precursor, have been stereoselectively glycosylated to give an orthogonally protected cellobiose disaccharide. Selective deprotection and sulfation allowed the syntheses of four differentially sulfated disaccharides, which have been characterized by NMR, HRMS and MS/MS. Together with their partially protected precursors, the new

  天然硫酸化聚糖是通过 TLR4 激活引起炎症的关键因素；因此，合成的外源硫酸糖可用于下调炎症过程。我们基于能够穿过血脑屏障的小型且具有生物相容性的碳水化合物，设计并合成了新的硫酸化化合物。从独特的前体获得的合适的受保护的供体和受体已被立体选择性糖基化，得到正交保护的纤维二糖二糖。选择性脱保护和硫酸化可以合成四种不同硫酸化的二糖，并通过 NMR、HRMS 和 MS/MS 对其进行了表征。新化合物与其部分受保护的前体一起在 HEK-TLR4 细胞上进行了测试。我们的结果显示了小寡糖调节 TLR4 活性的潜力，证实了硫酸化的必要性以及 6-硫酸基团在触发 TLR4 信号传导方面的关键作用。
• A method for the selective reduction of carbohydrate 4,6-O-benzylidene acetals
  作者：Michael P. DeNinno、John B. Etienne、Kimberly C. Duplantier

  DOI：10.1016/0040-4039(94)02348-f

  日期：1995.1

  Glucose-derived 4,6-O-benzylidene acetals can be selectively reduced to the corresponding 6-O-benzyl derivatives by the treatment with trifluoroacetic acid and triethylsilane.
• Hydroxymethyl Rotamer Populations in Disaccharides
  作者：Alfredo Roën、Juan I. Padrón、Jesús T. Vázquez

  DOI：10.1021/jo026913o

  日期：2003.6.1

  Sixteen methyl glucopyranosyl glucopyranoside disaccharides (methyl beta-D-Glcp(p-Br-Bz)-(1-->alpha)-beta/alpha-D-Glcp) containing beta-glycosidic linkages (1-->2, 1-->3, 1-->4, and 1-->6) were synthesized and analyzed by means of CD and NMR spectroscopy in three different solvents. For each of these four types of disaccharides, a correlation was observed between the hydroxymethyl rotational populations around the C5-C6 bond of the glucopyranosyl residue II with the substituents and the anomeric configuration of the methoxyl group in residue I, as well as with the solvent. Nonbonded interactions, the stereoelectronic exo-anomeric effect, and hydrogen bonding were found to be responsible for the observed rotameric differences. Whereas the rotational populations of the (1-->6)-linked disaccharides are mainly dependent on the exo-anomeric effect, the (1-->2)-bonded disaccharides are strongly dependent on the anomeric configuration at C1, and the (1-->3)- and (1-->4)-linked disaccharides are mainly dependent on the substituents and the solvent. The population of the gt rotamer decreases as nonbonded interactions increase but increases as the exo-anomeric effect becomes greater, as well as in the presence of intramolecular hydrogen bonding to the endocyclic oxygen O5'. Comparison of the hydroxymethyl rotational preferences between our model disaccharides revealed a dependence on the glycosidic linkage type. Thus the population of the gg and gt rotamers decreases/increases from (1-->2)-(beta series), to (1-->6)-, to (1-->2)-(alpha series), to (1-->4)-, and to (1-->3)-bonded disaccharides respectively, while the tg rotamer population remains almost constant (around 20%), except for the (1-->3)- and (1-->4)-linked disaccharides with the intramolecular hydrogen bonding to O5', where this population decreases to 10%.