methyl 6-O-(2,3,4,6-tetrakis-O-(p-bromobenzoyl)-β-D-glucopyranosyl)-2,3,4-tri-O-benzyl-β-D-glucopyranoside | 166769-06-8

• 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 6-O-(2,3,4,6-tetrakis-O-(p-bromobenzoyl)-β-D-glucopyranosyl)-2,3,4-tri-O-benzyl-β-D-glucopyranoside
• 英文别名: [(2R,3R,4S,5R,6R)-3,4,5-tris[(4-bromobenzoyl)oxy]-6-[[(2R,3R,4S,5R,6R)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]oxan-2-yl]methyl 4-bromobenzoate
• CAS: 166769-06-8
• 化学式: C₆₂H₅₄Br₄O₁₅
• 分子量: 1358.72
• InChiKey: JHRQZUYPDXKRMU-STQDLUFUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13
• 重原子数：
  81
• 可旋转键数：
  26
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  170
• 氢给体数：
  0
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  methyl 6-O-(2,3,4,6-tetrakis-O-(p-bromobenzoyl)-β-D-glucopyranosyl)-2,3,4-tri-O-benzyl-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 6-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 咪唑 、 四丁基氟化铵 、 silver trifluoromethanesulfonate 、 sodium hydride 、 1,1,3,3-四甲基脲 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 39.5h， 生成 methyl 6-O-(2,3,4,6-tetrakis-O-(p-bromobenzoyl)-β-D-glucopyranosyl)-2,3,4-tri-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

• Ferric chloride: An excellent reagent for the removal of benzyl ethers in the presence of p-bromobenzoate esters
  作者：Juan I. Padrón、Jesús T. Vázquez

  DOI：10.1016/0957-4166(95)00088-7

  日期：1995.4

  Anhydrous FeCl3 in dry CH2Cl2 removed benzyl ethers from carbohydrates containing p-bromobenzoate esters, without hydrogenolysis of the bromine atoms. In addition, debenzylations of β-glycopyranosides occurred with simultaneous anomerization or retention of the anomeric configuration.

  在干燥的CH 2 Cl 2中的无水FeCl 3从含有对溴苯甲酸酯的碳水化合物中除去苄基醚，而不会氢解溴原子。另外，β-糖吡喃糖苷的脱苄基反应同时发生异头异构化或异头构型的保留。