2,3-Bis-O-(p-bromobenzoyl)-4,6-bis-O-(p-methoxycinnamoyl)-α-D-glucopyranosyl bromide

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: 2,3-Bis-O-(p-bromobenzoyl)-4,6-bis-O-(p-methoxycinnamoyl)-α-D-glucopyranosyl bromide
• 英文别名: [(2R,3R,4S,5R,6R)-2-bromo-3-(4-bromobenzoyl)oxy-5-[(E)-3-(4-methoxyphenyl)prop-2-enoyl]oxy-6-[[(E)-3-(4-methoxyphenyl)prop-2-enoyl]oxymethyl]oxan-4-yl] 4-bromobenzoate
• 化学式: C₄₀H₃₃Br₃O₁₁
• 分子量: 929.407
• InChiKey: PXZDHHZYRZXLSX-LEXSOEINSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.4
• 重原子数：
  54
• 可旋转键数：
  17
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  133
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  D-薄荷醇 、 2,3-Bis-O-(p-bromobenzoyl)-4,6-bis-O-(p-methoxycinnamoyl)-α-D-glucopyranosyl bromide 在 silver trifluoromethanesulfonate 、 1,1,3,3-四甲基脲 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以52%的产率得到(1S,2R,5S)-(+)-1-Menthyl 2,3-bis-O-(p-bromobenzoyl)-4,6-bis-O-(p-methoxycinnamoyl)-β-D-glucopyranoside
  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
• 作为产物：
  描述：

  1,2,3-Tris-O-(p-bromobenzoyl)-4,6-bis-O-(p-methoxycinnamoyl)-D-glucopyranoside 在 氢溴酸 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 以85%的产率得到2,3-Bis-O-(p-bromobenzoyl)-4,6-bis-O-(p-methoxycinnamoyl)-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

• 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.