1,2,3-Tris-O-(p-bromobenzoyl)-D-glucopyranose | 210159-21-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,2,3-Tris-O-(p-bromobenzoyl)-D-glucopyranose
• CAS: 210159-21-0
• 化学式: C₂₇H₂₁Br₃O₉
• 分子量: 729.17
• InChiKey: XIKHRBZSGFLGGK-CXHBAANASA-N

反应信息

• 作为反应物：
  描述：

  (2E)-3-(4-甲氧基苯基)丙烯酰氯 、 1,2,3-Tris-O-(p-bromobenzoyl)-D-glucopyranose 在 4-二甲氨基吡啶 吡啶 作用下， 生成 1,2,3-Tris-O-(p-bromobenzoyl)-4,6-bis-O-(p-methoxycinnamoyl)-β-D-glucopyranoside 、 1,2,3-Tris-O-(p-bromobenzoyl)-4,6-bis-O-(p-methoxycinnamoyl)-α-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：

  4,6-O-Benzylidene-1,2,3-tris-O-(p-bromobenzoyl)-D-glucopyranoside 在 对甲苯磺酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 以89%的产率得到1,2,3-Tris-O-(p-bromobenzoyl)-D-glucopyranose
  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

• Stereochemical study of the CD spectral differences between anomers of alkyl glucopyranosides
  作者：Juan I Padrón、Jesús T Vázquez

  DOI：10.1016/s0957-4166(98)00037-8

  日期：1998.2

  Slightly different chair conformation geometries were demonstrated to be the origin of the CD spectral differences observed in anomers of alkyl glucopyranosides. The study, using methyl glucopyranoside derivatives as model compounds, showed excellent agreement between CD data, 1H NMR data, and semiempirical calculations, and the geometries found explained satisfactorily the higher amplitudes observed

  椅子构型的几何形状略有不同，这是在烷基吡喃葡萄糖苷的异构体中观察到的CD光谱差异的根源。该研究使用甲基吡喃葡萄糖苷衍生物作为模型化合物，显示出CD数据，1 H NMR数据和半经验计算之间的优异一致性，并且发现的几何形状令人满意地解释了四色取代的烷基吡喃葡萄糖苷的β-端基异构体观察到的更高振幅。涉及C2上的发色团的2 / 3、2 / 4和2/6的成对相互作用最依赖于端基异构构型，2/4相互作用甚至显示出异头异构体的相反CD符号。另外，发现2/3成对相互作用独立于糖苷配基的结构性质。