1,2,3,4-tetra-O-acetyl-6-deoxy-6-fluoro-β-D-galactopyranose | 118396-37-5

• 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: 1,2,3,4-tetra-O-acetyl-6-deoxy-6-fluoro-β-D-galactopyranose
• 英文别名: 1,2,3,4-tetra-O-acetyl-6-fluoro-6-deoxy-D-galactose；[(2S,3R,4S,5R,6S)-4,5,6-triacetyloxy-2-(fluoromethyl)oxan-3-yl] acetate
• CAS: 118396-37-5
• 化学式: C₁₄H₁₉FO₉
• 分子量: 350.298
• InChiKey: NGYYXVXMDLMRLI-MBJXGIAVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.04
• 重原子数：
  24.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  114.43
• 氢给体数：
  0.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  1,2,3,4-tetra-O-acetyl-6-deoxy-6-fluoro-β-D-galactopyranose 在 N-甲基咪唑 、 氢溴酸 、 溶剂黄146 、 锌 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， 生成 3,4-di-O-acetyl-6-deoxy-6-fluoro-D-galactal
  参考文献：
  名称：

  肿瘤相关碳水化合物和糖肽抗原的氟化类似物的合成

  摘要：

  肿瘤相关粘蛋白糖蛋白的部分结构是开发选择性抗癌疫苗的有趣目标结构。为了探究氟化对粘蛋白糖肽的免疫学和代谢特性的影响，已经合成了六种新型氟化糖基-苏氨酸缀合物。正交保护的糖基氨基酸的合成是在关键的氟化和糖基化步骤中使用微波辐射来实现的。2'-deoxy-2'-fluoro- 和 6'-deoxy-6'-fluoro-T 抗原构建块被应用于通过 SPPS 合成 MUC1 串联重复-糖肽抗原的类似物。

  DOI：

  10.1055/s-0029-1217566
• 作为产物：
  描述：

  Α-D-乳酸吡喃糖苷甲酯 在 二乙胺基三氟化硫 、 水 、 sodium acetate 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 11.5h， 生成 1,2,3,4-tetra-O-acetyl-6-deoxy-6-fluoro-β-D-galactopyranose
  参考文献：
  名称：

  UDP-6-deoxy-6-fluoro-α-d-galactose binds to two different galactosyltransferases, but neither can effectively catalyze transfer of the modified galactose to the appropriate acceptor

  摘要：

  The effect of substitution of the HO-6 of D-galactose with fluorine on the ability of alpha-(1 --> 3)-galactosyltransferase (EC 2.4.1.151) and beta-(1 --> 4)-galactosyltransferase (EC 2.4.1.22) to catalyze its transfer from UDP to an appropriate acceptor was determined. HPLC analyses indicated that each transferase properly catalyzed formation of the expected product [beta-D-Gal-(1 --> 4)-D-GlcNAc for the beta-(1 --> 4)-galactosyltransferase and alpha-D-Gal-(1 --> 3)-beta-D-Gal-(1 --> 4)-D-GlcNAc for the alpha-(1 --> 3)-D-galactosyltransferase] when UDP-alpha-D-Gal was the substrate. When UDP-6-deoxy-6-fluoro-alpha-D-galactose (6) was used in conjunction with each transferase, no product indicative of transfer of 6-deoxy-6-fluoro-D-galactose to its respective acceptor sugar was identified. 6-Deoxy-6-fluoro-D-galactose (3) was obtained by hydrolysis of methyl 6-deoxy-6-fluoro-alpha-D-galactopyranoside, synthesized by the selective fluorination of methyl alpha-D-galactopyranoside with diethylaminosulfur trifluoride (DAST), with aqueous trifluoroacetic acid. Acetylation of 3 gave crystalline 1,2,3,4-tetra-O-acetyl-6-deoxy-6-fluoro-beta-D-galactopyranose, which was converted to the corresponding 1-alpha-phosphate and used for the synthesis of 6. (C) 1999 Published by Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(99)00104-4

文献信息

• The Role of Sugar Substituents in Glycoside Hydrolysis
  作者：Mark N. Namchuk、John D. McCarter、Adam Becalski、Trevor Andrews、Stephen G. Withers

  DOI：10.1021/ja992044h

  日期：2000.2.1

  used to probe the mechanism of spontaneous β-glycoside hydrolysis. Their relative rates of hydrolysis followed the order 2-deoxy > 4-deoxy > 3-deoxy ≈ 6-deoxy > parent > 6-deoxy-6-fluoro > 3-deoxy-3-fluoro > 4-deoxy-4-fluoro > 2-deoxy-2-fluoro. Hammett correlations of the pH-independent hydrolysis rates of each of the 6-, 4-, 3-, and 2-position substituted glycosides with the σI value for the sugar

  合成了一系列单取代的脱氧和脱氧氟 2,4-二硝基苯基 (DNP) β-d-吡喃糖苷，并用于探索自发 β-糖苷水解的机制。它们的相对水解速率顺序为 2-脱氧 > 4-脱氧 > 3-脱氧 ≈ 6-脱氧 > 母体 > 6-脱氧-6-氟 > 3-脱氧-3-氟 > 4-脱氧-4-氟 > 2-脱氧-2-氟。6 位、4 位、3 位和 2 位取代糖苷的 pH 无关水解速率与糖环取代基的 σI 值的哈米特相关性是线性的（r = 0.95 至 0.999，ρI = -2.2到-10.7），这与水解速率主要取决于对缺电子过渡态的场效应。正如 Kirkwood-Westheimer 模型预测的那样，DNP 糖苷的相对水解速率可以根据类氧碳鎓离子过渡态的稳定性进行合理化。一系列内水解速率的主要决定因素似乎是环取代基的场效应……