phenyl (5-acetamido-3,5-dideoxy-D-glycero-β-D-galacto-non-2-ulopyranosylonic acid) | 15964-33-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl (5-acetamido-3,5-dideoxy-D-glycero-β-D-galacto-non-2-ulopyranosylonic acid)
• 英文别名: phenyl β-D-sialoside；phenyl β-D-N-acetylneuraminide；Ph-βNeuAc；NeuAc(b)-O-Ph；(2R,4S,5R,6R)-5-acetamido-4-hydroxy-2-phenoxy-6-[(1R,2R)-1,2,3-trihydroxypropyl]oxane-2-carboxylic acid
• CAS: 15964-33-7
• 化学式: C₁₇H₂₃NO₉
• 分子量: 385.371
• InChiKey: FLOVUNWVDMMYKY-CXECBNLGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.1
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  166
• 氢给体数：
  6
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  methyl [phenyl(5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-β-D-galacto-non-2-ulopyranosyl)]onate 在 lithium hydroxide 、 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 0.5h， 生成 phenyl (5-acetamido-3,5-dideoxy-D-glycero-β-D-galacto-non-2-ulopyranosylonic acid)
  参考文献：
  名称：

  Unexpected Stability of Aryl β-N-Acetylneuraminides in Neutral Solution:  Biological Implications for Sialyl Transfer Reactions

  摘要：

  A reagent panel comprised of seven aryl beta-D-N-acetylneuraminides was synthesized and then used to probe the mechanisms of nonenzymatic hydrolysis. These reactions proceeded via four independent pathways: (1) acid-catalyzed hydrolysis of the neutral molecule; (2) acid-catalyzed hydrolysis of the anionic form, or its kinetic equivalent spontaneous hydrolysis of the neutral form; (3) spontaneous hydrolysis of the anionic form; and (4) a base-promoted pathway. The pH-independent spontaneous hydrolysis of 4-nitrophenyl alpha-D-N-acetylneuraminide (5) occurs at a rate that is over 100 times faster than that of the corresponding reaction of 4-nitrophenyl O-D-N-acetylneuraminide (4a). Spontaneous hydrolyses of four aryl beta-D-N-acetylneuraminides displayed a beta(lg) value of -1.24 +/- 0.16 (pH = 8.1, T= 100 degrees C), and at a pH value of 1.0 (50 degrees C), all seven panel members gave a beta(lg) value of 0.14 +/- 0.08. The aqueous ethanolyses of 4a and 5 gave similar products and displayed sensitivity parameters (m) in a standard Winstein-Grunwald analysis of -0.04 +/- 0.01 and +0.23 +/- 0.02, respectively. These results, plus the activation parameters calculated for the spontaneous hydrolyses of the anionic forms of 5 (Delta H = 116 +/- 2 U mol(-1) and Delta S = 27 +/- 4 J mol(-1) K-1) and 4a (Delta H = 138 3 U mol(-1) and AS = 59 +/- 8 J mol(-1) K-1), are inconsistent with anomeric carboxylate assistance occurring during the hydrolysis reactions, and the likely cause for the enhanced reactivity of 5 in comparison to that of 4a is an increase in ground-state steric strain.

  DOI：

  10.1021/ja042280e

文献信息

• Brønsted Analysis of an Enzyme-Catalyzed Pseudo-Deglycosylation Reaction: Mechanism of Desialylation in Sialidases
  作者：Fahimeh S. Shidmoossavee、Lydia Cheng、Jacqueline N. Watson、Andrew J. Bennet

  DOI：10.1021/bi100513u

  日期：2010.8.3

  the 3,5-difluoro compound undergoes catalyzed hydrolysis exceedingly slowly. These observations, taken with solvent deuterium kinetic isotope effects (kH2O/kD2O) on the catalyzed hydrolysis of the 2-fluorophenyl substrate of 0.88 ± 0.24 (kcat/Km) and 1.16 ± 0.12 (kcat) and the poor inhibition shown by phenol (IC50 > 1 mM), are consistent with glycosidic C−O cleavage being rate determining for both kcat/Km

  在小单孢viridifaciens Y370G反相唾液酸酶突变体已被发现具有β-唾液酸酶与各种氟-取代的苯基β-唾液酸糖苷酶活性。七甲试剂面板单-和二氟苯基β- d -sialosides合成，和使用这些化合物，在结合亲苯基β- d -sialoside，探测的机构M. viridifaciens Y370G突变体的唾液酸酶催化的水解。这些水解反应模拟了在相应的野生型唾液酸酶反应过程中形成的关键的酪氨酸酶结合中间体的去糖基化反应步骤。在k cat / K上导出的Brønsted参数（βlg）对于显示出显着活性的四种底物，m为-0.46±0.02，并且这些底物涵盖一系列离去基团能力（通过其共轭酸的p K a介于7.09和9.87之间判断）。4-氟，2,3-和2,5-二氟底物的活性降低，而3,5-二氟化合物的催化水解非常缓慢。这些观察结果是采用溶剂氘动力学同位素效应（k H 2 O / k D