4,6-O-benzylidene-1,2,3-tris-O-acetyl-D-galactopyranoside | 243136-79-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: 4,6-O-benzylidene-1,2,3-tris-O-acetyl-D-galactopyranoside
• 英文别名: 1,2,3-tri-O-acetyl-4,6-O-benzylidene-D-galactopyranose
• CAS: 243136-79-0
• 化学式: C₁₉H₂₂O₉
• 分子量: 394.378
• InChiKey: MMMFFJBLSNOZRA-RCSSLFFRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.25
• 重原子数：
  28.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  106.59
• 氢给体数：
  0.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  4,6-O-benzylidene-1,2,3-tris-O-acetyl-D-galactopyranoside 在 吡啶 、 4-二甲氨基吡啶 、 水 、 氢溴酸 、 silver trifluoromethanesulfonate 、 溶剂黄146 、 1,1,3,3-四甲基脲 作用下， 以 二氯甲烷 为溶剂， 生成 (1R,2S,5R)-(-)-1-menthyl 2,3-bis-O-acetyl-4,6-bis-O-(p-bromobenzoyl)-β-D-galactopyranoside
  参考文献：
  名称：

  Alkyl Galactopyranosides:  Rotational Population Dependence of the Hydroxymethyl Group on the Aglycon and Its Absolute Configuration and on the Anomeric Configuration

  摘要：

  The rotational populations of the hydroxymethyl group in chiral and nonchiral alkyl alpha- and beta-galactopyranosides proved, on the basis of circular dichroism (CD) and H-1 NMR data, to be dependent on the structure of the aglycon: the population of the gt and tg rotamers increased and decreased, respectively, as the pK(a) of the bonded alcohol (aglycon) increased, while the population of the gg rotamer remained practically constant. Furthermore, low-temperature CD measurements proved that the most stable rotamer is the gt, and not the tg. In addition, a clear correlation between the rotational populations and the absolute configuration of the chiral aglycon was observed; namely, higher and smaller gt and tg populations were observed for the (S)-alkyl beta-D-galactopyranosides than for their (R)-alkyl beta-D-galactopyranoside counterparts, the opposite behavior being observed for the cl-anomers. The results point to the exo anomeric effect as being responsible for these rotational dependencies, as well as to nonbonding interactions between the aglycon and the chromophore at C6 for those stereoisomers having in their aglycon a bulky substituent syn to the endocyclic oxygen (O5). In addition, the chemical shift differences (Delta delta) of the aglyconic protons of galactosylated chiral alcohols proved to be characteristic of the absolute configuration of the bonded chiral alcohol.

  DOI：

  10.1021/jo981002t
• 作为产物：
  描述：

  苯甲醛二甲缩醛 在 吡啶 、 对甲苯磺酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 4,6-O-benzylidene-1,2,3-tris-O-acetyl-D-galactopyranoside
  参考文献：
  名称：

  Alkyl Galactopyranosides:  Rotational Population Dependence of the Hydroxymethyl Group on the Aglycon and Its Absolute Configuration and on the Anomeric Configuration

  摘要：

  The rotational populations of the hydroxymethyl group in chiral and nonchiral alkyl alpha- and beta-galactopyranosides proved, on the basis of circular dichroism (CD) and H-1 NMR data, to be dependent on the structure of the aglycon: the population of the gt and tg rotamers increased and decreased, respectively, as the pK(a) of the bonded alcohol (aglycon) increased, while the population of the gg rotamer remained practically constant. Furthermore, low-temperature CD measurements proved that the most stable rotamer is the gt, and not the tg. In addition, a clear correlation between the rotational populations and the absolute configuration of the chiral aglycon was observed; namely, higher and smaller gt and tg populations were observed for the (S)-alkyl beta-D-galactopyranosides than for their (R)-alkyl beta-D-galactopyranoside counterparts, the opposite behavior being observed for the cl-anomers. The results point to the exo anomeric effect as being responsible for these rotational dependencies, as well as to nonbonding interactions between the aglycon and the chromophore at C6 for those stereoisomers having in their aglycon a bulky substituent syn to the endocyclic oxygen (O5). In addition, the chemical shift differences (Delta delta) of the aglyconic protons of galactosylated chiral alcohols proved to be characteristic of the absolute configuration of the bonded chiral alcohol.

  DOI：

  10.1021/jo981002t

文献信息

• Synthesis of a sialyl-α-(2→6)-lactosamine trisaccharide with a 5-amino-3-oxapentyl spacer group at C-1I
  作者：Santiago Figueroa-Pérez、Vicente Vérez-Bencomo

  DOI：10.1016/s0008-6215(99)00022-1

  日期：1999.4

  As part of a continuing study aimed to achieve improved monoclonal antibodies against carcinoembryonic antigen (CEA) carbohydrate fragments, the synthesis of a sialyl-(2-->6)-lactosamine trisaccharide with a 5-amino-3-oxapentyl spacer group at C-1I has been developed. Two different routes to access this target are described. For this purpose 5-azido-3-oxapentyl 6-O-benzyl-2-deoxy-2-phthalimido-beta-D-glucopyranoside

  作为旨在获得改进的针对癌胚抗原（CEA）碳水化合物片段的单克隆抗体的持续研究的一部分，合成了在C位带有5-氨基-3-氧杂戊基间隔基的唾液酸-（2-> 6）-乳糖胺三糖-1I已开发。描述了访问此目标的两种不同途径。为此目的，使用结晶的2,3-二-以5-羟甲基化的方式将5-叠氮基-3-氧杂戊基6-O-苄基-2-脱氧-2-邻苯二甲酰亚胺基-β-D-吡喃葡萄糖苷（4）以81％的产率选择性地β-半乳糖基化。 O-乙酰基-4,6-O-亚苄基-α-D-吡喃半乳糖基三氯乙酰亚氨酸酯为供体，利用C-2为4的庞大邻苯二甲酰亚胺基。另一方面，合适的受保护受体5-叠氮基的半乳糖基化-3-氧杂戊基2-乙酰氨基-3,6-二-O-苄基-2-脱氧-β-D-吡喃葡萄糖苷与结晶的2,3-二-O-乙酰基-4，6-O-亚苄基-α-D-半乳糖基溴化物以中等58％的产率提供了相应的二糖。尽管第一种策略与第二种策略不同，但实际上需要在
• Synthesis of Ganglioside Mimics for Binding Studies with Myelin‐Associated Glycoprotein (MAG)*
  作者：Sascha Janssen、Richard R. Schmidt

  DOI：10.1080/07328300500176312

  日期：2005.8

  Glycosylation of 3‐O‐unprotected 2‐azido‐2‐deoxy‐galactopyranoside (compound 5) with O‐(2,3‐di‐O‐acyl‐4,6‐O‐benzylidene‐D‐galactopyranosyl) trichloroacetimidates (compounds 4A, B) as glycosyl donors afforded β (1–3)‐linked disaccharides (9A, B) in high yield. Removal of the 2,3‐O‐acyl groups and selective 3‐O‐alkylation with α‐benzyloxycarbonyl‐alkyl triflates furnished the protected target molecules

  3-O-未保护的2-叠氮基-2-脱氧-吡喃半乳糖苷（化合物5）与O-（2,3-二-O-酰基-4,6-O-亚苄基-D-吡喃半乳糖基）三氯乙酰胺基糖苷（化合物4A） ，B）作为糖基供体，以高收率提供了与β（1-3）连接的二糖（9A，B）。去除2,3-O-酰基和用α-苄氧基羰基烷基三氟甲磺酸酯进行选择性3-O-烷基化提供了受保护的目标分子，这些分子很容易转化为所需的神经节苷脂模拟物。*致敬已故的雅克·H·范·布姆教授。
• Greilich, Ulrike; Zimmermann, Peter; Jung, Karl-Heinz, Liebigs Annalen der Chemie, 1993, # 8, p. 859 - 864
  作者：Greilich, Ulrike、Zimmermann, Peter、Jung, Karl-Heinz、Schmidt, Richard R.

  DOI：——

  日期：——