2,3,4,6-Tetrakis-O-(p-bromobenzoyl)-α-D-glucopyranosyl bromide | 123505-65-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,3,4,6-Tetrakis-O-(p-bromobenzoyl)-α-D-glucopyranosyl bromide
• 英文别名: [(2R,3R,4S,5R,6R)-6-bromo-3,4,5-tris[(4-bromobenzoyl)oxy]oxan-2-yl]methyl 4-bromobenzoate
• CAS: 123505-65-7
• 化学式: C₃₄H₂₃Br₅O₉
• 分子量: 975.071
• InChiKey: JSFWTNOFRZDHQD-RLXMVLCYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10
• 重原子数：
  48
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  2,3,4,6-Tetrakis-O-(p-bromobenzoyl)-α-D-glucopyranosyl bromide 在 silver trifluoromethanesulfonate 、 三氯化铁 、 1,1,3,3-四甲基脲 作用下， 以 吡啶 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 methyl 6-O-(2,3,4,6-tetrakis-O-(p-bromobenzoyl)-β-D-glucopyranosyl)-2,3,4-tri-O-acetyl-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：

  1,2,3,4,6-Pentakis-O-(p-bromobenzoyl)-D-glucopyranoside 在 氢溴酸 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 以89%的产率得到2,3,4,6-Tetrakis-O-(p-bromobenzoyl)-α-D-glucopyranosyl bromide
  参考文献：
  名称：

  CD and 1H NMR Study of the Rotational Population Dependence of the Hydroxymethyl Group in .beta. Glucopyranosides on the Aglycon and Its Absolute Configuration

  摘要：

  The rotamer population around the C5-C6 bond of chiral and nonchiral alkyl P-D-glucopyranoside derivatives proved to be dependent on the structure of the aglycon; the population of the gg and gt rotamers decreased and increased, respectively, as the pK(a) of the aglycon increased, whereas the rs tg population remained almost constant. In addition, the rotamer populations correlate with the absolute configuration of the aglyconic carbons, namely, higher CD A values and smaller (3)J(H5,H6R) coupling constants are obtained for the (R)-alkyl glucopyranosides than for their (S)-alkyl glucopyranoside counterparts, as the result of increased and decreased gg and gt populations, respectively. The results show a clear relationship between the rotamer distributions and the stereoelectronic exo-anomeric effect. Asa consequence of these findings the absolute configuration of secondary alcohols can be determined, a single enantiomer being necessary for this purpose.

  DOI：

  10.1021/jo00113a038

文献信息

• Microscale glycosidic cleavage of oligosaccharide bromobenzoates for circular dichroism analysis
  作者：Makoto Ojika、Harold V. Meyers、Mayland Chang、Koji Nakanishi

  DOI：10.1021/ja00206a042

  日期：1989.11

  La degradation chimique de la digitonine avec une solution de bromure de l'acide bromo acetique donne des halogenures d'hexo (ou pento) pyranosyles bromobenzoyles ou bromoacetyles qui sont ensuite transformes en O-methyl-1 hexo (ou pento) pyranosides bromobenzoyles et methoxy-4 cinnamoyles

  La 降解 chimique de la digitonine avec une 溶液 de bromure de l'acide bromo acetique donne des haloures d'hexo (ou pento) pyranosyles bromobenzoyles ou bromoacetyles quisont ensuitetransformes en O-methyl-1 hexo (ou pento) pyranosides et bromobenzoyles -4 肉桂
• OJIKA, MAKOTO;MEYERS, HAROLD V.;CHANG, MAYLAND;NAKANISHI, KOJI, J. AMER. CHEM. SOC., 111,(1989) N4, C. 8944-8946
  作者：OJIKA, MAKOTO、MEYERS, HAROLD V.、CHANG, MAYLAND、NAKANISHI, KOJI

  DOI：——

  日期：——
• CD and 1H NMR Study of the Rotational Population Dependence of the Hydroxymethyl Group in .beta. Glucopyranosides on the Aglycon and Its Absolute Configuration
  作者：Ezequiel Q. Morales、Juan I. Padron、Mar Trujillo、Jesus T. Vazquez

  DOI：10.1021/jo00113a038

  日期：1995.4

  The rotamer population around the C5-C6 bond of chiral and nonchiral alkyl P-D-glucopyranoside derivatives proved to be dependent on the structure of the aglycon; the population of the gg and gt rotamers decreased and increased, respectively, as the pK(a) of the aglycon increased, whereas the rs tg population remained almost constant. In addition, the rotamer populations correlate with the absolute configuration of the aglyconic carbons, namely, higher CD A values and smaller (3)J(H5,H6R) coupling constants are obtained for the (R)-alkyl glucopyranosides than for their (S)-alkyl glucopyranoside counterparts, as the result of increased and decreased gg and gt populations, respectively. The results show a clear relationship between the rotamer distributions and the stereoelectronic exo-anomeric effect. Asa consequence of these findings the absolute configuration of secondary alcohols can be determined, a single enantiomer being necessary for this purpose.
• 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%.