5-acetamido-4,7,8,9-tetra-O-acetyl-2,3,5-trideoxy-2-fluoro-D-glycero-α-D-galacto-2-nonulosonic acid methyl ester | 91041-78-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-acetamido-4,7,8,9-tetra-O-acetyl-2,3,5-trideoxy-2-fluoro-D-glycero-α-D-galacto-2-nonulosonic acid methyl ester
• 英文别名: methyl (5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2-fluoro-β-D-glycero-D-galacto-2-nonulopyranosid)onate
• CAS: 91041-78-0
• 化学式: C₂₀H₂₈FNO₁₂
• 分子量: 493.44
• InChiKey: ZNDKGFJFQUIEPD-DCDDNHAVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.52
• 重原子数：
  34.0
• 可旋转键数：
  9.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  169.83
• 氢给体数：
  1.0
• 氢受体数：
  12.0

反应信息

• 作为反应物：
  描述：

  5-acetamido-4,7,8,9-tetra-O-acetyl-2,3,5-trideoxy-2-fluoro-D-glycero-α-D-galacto-2-nonulosonic acid methyl ester 在 lithium hydroxide 、 4 A molecular sieve 、 三氟化硼乙醚 、 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 3-methylphenyl (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
• 作为产物：
  描述：

  4,7,8,9-四-O-乙酰基-N-乙酰神经氨酸甲酯 在 氢氟酸 作用下， 以 吡啶 为溶剂， 反应 4.0h， 生成 5-acetamido-4,7,8,9-tetra-O-acetyl-2,3,5-trideoxy-2-fluoro-D-glycero-α-D-galacto-2-nonulosonic acid methyl ester
  参考文献：
  名称：

  Synthesis and Characterization of an Anomeric Sulfur Analogue of CMP-Sialic Acid

  摘要：

  alpha-2,3-Sialyltransferase catalyzes the transfer of sialic acid from CMP-sialic acid (1) to a lactose acceptor. An analogue of 1 was synthesized in which the anomeric oxygen atom was replaced with a sulfur atom (1S). The key step in the synthesis of 1S was a tetrazole-promoted coupling of a cytidine-5'-phosphoramidite with a glycosyl thiol of a protected sialic acid. Compounds 1 and 1S were characterized for their activity in a sialyl transfer assay. The rate of solvolysis in aqueous buffer of analogue 1S was 50-fold slower than that of 1. Analogue 1S was found to be substrate for alpha-2,3-sialyltransferase. The K-m of 1S was just 3-fold higher than that of 1, while the k(cat) of 1S was 2 orders of magnitude lower compared to 1.

  DOI：

  10.1021/jo000646+

文献信息

• A facile and convenient synthesis of disarmed glycosyl fluorides using in situ-generated iodine monofluoride (see Ref. 1)
  作者：G. Mugunthan、K. P. Ravindranathan Kartha

  DOI：10.1016/j.tetlet.2012.08.024

  日期：2012.10

  A facile and convenient synthesis of disarmed glycosyl fluorides using in situ-generated iodine monofluoride is reported. The method is tolerant to most of the popularly used protecting groups and gives exclusively the α-anomeric product in very good yields.

  据报道，使用原位生成的一氟化碘可以轻松，方便地合成解除武装的糖基氟化物。该方法耐受大多数常用的保护基团，并且以非常好的收率仅得到α-异头物产物。
• Synthesis and conformational studies of 2-β-chloro, 2-α-fluoro, and 2-β-fluoro derivatives of 2-deoxy-N-acetyl-neuraminic acid
  作者：Mahendra N. Sharma、Ronald Eby

  DOI：10.1016/0008-6215(84)85354-9

  日期：1984.4

  -2-nonulosonic acid methyl esters and the β-chloro analog were synthesized from N -acetylneuraminic acid. Their 1 H- and 13 C-n.m.r. spectra were completely assigned by using single-frequency decoupling, off-resonance decoupling, and spin-simulation programs. Bond angles estimated from the 1 H coupling-constants indicate that all of the compounds adopt the 2 C 5 ( l ) conformation with minor conformational differences

  摘要5-Acetamido-4,7,8,9-tetra-O -acetyl-2,3,5-trideoxy-2-fluoro-d-glycero-α-and-β-d-galacto-2-nonulosonicacidmethyl由N-乙酰神经氨酸合成酯和β-氯类似物。他们的1 H和13 Cn.mr光谱通过使用单频去耦，失谐去耦和自旋模拟程序来完全分配。由1 H耦合常数估算的键角表明，所有化合物均采用2 C 5（l）构象，而C 3侧链的构象差异较小。还制备了5-乙酰基-2,3,5-三-脱氧-2-氟-d-甘油-α-和-β-d-半乳糖-2-壬基磺酸及其甲酯。