methyl 3-O-(2,3,4,6-tetrakis-O-(p-bromobenzoyl)-β-D-glucopyranosyl)-β-D-glucopyranoside | 556814-94-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl 3-O-(2,3,4,6-tetrakis-O-(p-bromobenzoyl)-β-D-glucopyranosyl)-β-D-glucopyranoside
• 英文别名: [(2R,3R,4S,5R,6S)-3,4,5-tris[(4-bromobenzoyl)oxy]-6-[(2R,3R,4S,5R,6R)-3,5-dihydroxy-2-(hydroxymethyl)-6-methoxyoxan-4-yl]oxyoxan-2-yl]methyl 4-bromobenzoate
• CAS: 556814-94-9
• 化学式: C₄₁H₃₆Br₄O₁₅
• 分子量: 1088.34
• InChiKey: ZDYWQCVHLDNYDI-MGBNTCBZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  60
• 可旋转键数：
  17
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  203
• 氢给体数：
  3
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  methyl 3-O-(2,3,4,6-tetrakis-O-(p-bromobenzoyl)-β-D-glucopyranosyl)-β-D-glucopyranoside 在 三氯化铁 、 对甲苯磺酸 作用下， 以 吡啶 、 甲醇 、 二氯甲烷 为溶剂， 生成 methyl 3-O-(2,3,4,6-tetrakis-O-(p-bromobenzoyl)-β-D-glucopyranosyl)-α-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 silver trifluoromethanesulfonate 、 三氯化铁 、 sodium hydride 、 对甲苯磺酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 2.5h， 生成 methyl 3-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

文献信息

• Ferric chloride: a mild and versatile reagent for the formation of 1,6-anhydro glucopyranoses
  作者：Pedro O Miranda、Ignacio Brouard、Juan I Padrón、Jaime Bermejo

  DOI：10.1016/s0040-4039(03)00821-9

  日期：2003.5

  A novel method for the preparation of 1,6-anhydro glucopyranoses (mono- and disaccharides) utilizing anhydrous FeCl3 as Lewis acid is described. Treatment of methyl 6-O-benzyl and 6-O-p-methoxybenzyl-α/β d-glucopyranosides derivatives with FeCl3 in CH2Cl2 at room temperature and 40°C afforded 1,6-anhydro glucopyranosides in moderate to good yields, through a debenzylation and intramolecular glycosidation

  描述了一种利用无水FeCl 3作为路易斯酸制备1，6-脱水葡萄糖吡喃糖（单糖和二糖）的新方法。的治疗6- ø -苄基和6- ö - p甲氧基苄基- α/βd-吡喃葡萄糖苷与的FeCl衍生物3在CH 2氯2在室温和40℃下，得到1,6-脱水吡喃葡萄糖苷在中度至良好在一个步骤中通过脱苄基化和分子内糖苷化反应产生。提出了合理的反应途径。