methyl [phenyl(5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-β-D-galacto-non-2-ulopyranosyl)]onate | 855996-96-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl [phenyl(5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-β-D-galacto-non-2-ulopyranosyl)]onate
• 英文别名: methyl (2R,4S,5R,6R)-5-acetamido-4-acetyloxy-2-phenoxy-6-[(1S,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylate
• CAS: 855996-96-2
• 化学式: C₂₆H₃₃NO₁₃
• 分子量: 567.547
• InChiKey: AAUDGIPJQUSAMJ-UQJVNAJPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  40
• 可旋转键数：
  16
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  179
• 氢给体数：
  1
• 氢受体数：
  13

反应信息

• 作为反应物：
  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
• 作为产物：
  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 、 苯酚 在 4 A molecular sieve 、 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 以83%的产率得到methyl [phenyl(5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-β-D-galacto-non-2-ulopyranosyl)]onate
  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

• Glycosylation with ulosonates under Mitsunobu conditions: scope and limitations
  作者：Nándor Kánya、Sándor Kun、Gyula Batta、László Somsák

  DOI：10.1039/d0nj03044a

  日期：——

  A systematic study was performed by using Mitsunobu conditions (diethyl azodicarboxylate, Ph3P or n-Bu3P in THF or CH3CN) for glycosylations with methyl 3,4,5,7-tetra-O-benzoyl-α-D-gluco-hept-2-ulopyranosonate. From a set of 47 O-, N-, S- and C-nucleophiles, phenols and N-hydroxy compounds with a pKa of 5–8, phthalimide, benzotriazole, 6-chloropurine, an oxazolidinedione and several tetrazoles with

  通过使用Mitsunobu条件（在THF或CH 3 CN中的偶氮二羧酸二乙酯，Ph 3 P或n -Bu 3 P ）进行甲基，3,4,5,7-四-O-苯甲酰基-α- D的糖基化研究-葡萄糖-庚-2- ulopyranosonate。选自47种O-，N-，S-和C-亲核试剂，酚和N-羟基化合物，其ap K a为5-8，邻苯二甲酰亚胺，苯并三唑，6-氯嘌呤，恶唑烷二酮和若干具有ap K a的四唑苯酚的比例为4-8，而苯酚以中等到非常高的产率提供了相应的产物，而C-亲核试剂则没有反应性。对三卤代乙酰苯胺进行O-糖基化反应，得到O-糖基-N-芳基三卤代乙酰亚胺酸酯，这是常规的O-亚氨基化无法制备的。所有反应都是高度立体选择性的，仅产生β（D）异构体。用甲基（5-乙酰氨基-4,7,8,9-四- ø -乙酰基-3,5-二脱氧d -甘油基- d -半乳-2-壬基吡喃二酮酸）酚和苯并三唑生成了预期的产物，但
• Stereocontrolled Synthesis of Phenolic α-d-Glycopyranosides
  作者：Stephen Hanessian、Gabrielle St-Pierre、Laila Dafik、Ellen Klegraf

  DOI：10.1055/s-0035-1561461

  日期：——

  Dedicated to Professor Richard Schmidt for his seminal contributions to glycoside synthesis Abstract Adopting the ‘remote activation concept’ toward stereocontrolled glycoside synthesis with minimal use of protection groups, a general synthesis of phenolic 1,2-cis glycopyranosides is reported, as exemplified by aryl α-d-galacto-, α-d-gluco- and 2-azido α-d-glucopyranosides among others using glycosyl

  致力于Richard Schmidt教授对糖苷合成的开创性贡献 抽象的 据报道，采用“远程激活概念”，以最少的保护基使用立体控制的糖苷合成，已报道了酚类1,2-顺式糖吡喃糖苷的一般合成，例如芳基α- d-半乳糖基，α- d-葡萄糖基和2-叠氮基α- d-吡喃葡萄糖苷，尤其是使用带有异头（3-溴-2-吡啶氧基）基团并由三氟甲磺酸甲酯催化的糖基供体。 据报道，采用“远程激活概念”，以最少的保护基使用立体控制的糖苷合成，已报道了酚类1,2-顺式糖吡喃糖苷的一般合成，例如芳基α- d-半乳糖基，α- d-葡萄糖基和2-叠氮基α- d-吡喃葡萄糖苷，尤其是使用带有异头（3-溴-2-吡啶氧基）基团并由三氟甲磺酸甲酯催化的糖基供体。