methyl α-D-arabino-hexopyranosid-2-ulose | 39687-01-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl α-D-arabino-hexopyranosid-2-ulose
• 英文别名: methyl α-D-arabino-2-hexopyranosidulose；methyl 2-keto-α-D-glucopyranoside；Methyl-α-D-arabino-hexopyranosid-2-ulose；Methyl-α-D-arabino-hexopyranosidulose；Methyl I+/--D-arabino-hexopyranosid-2-ulose；(2S,4S,5S,6R)-4,5-dihydroxy-6-(hydroxymethyl)-2-methoxyoxan-3-one
• CAS: 39687-01-9
• 化学式: C₇H₁₂O₆
• 分子量: 192.169
• InChiKey: ISRHTFSJNHPZNP-CXXDYQFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.6
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  96.2
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl α-D-arabino-hexopyranosid-2-ulose 、 硼氢化钠 生成 alpha-甲基葡萄糖甙
  参考文献：
  名称：

  TSUDA, YOSHISUKE;HANAJIMA, MAKIKO;MATSUHIRA, NAOHISA;OKUNO, YUKIHIRO;KANE+, CHEM. AND PHARM. BULL., 37,(1989) N, C. 2344-2350

  摘要：

  DOI：
• 作为产物：
  描述：

  甲基-D-丙噻 在 phenyltrimethylammonium tribromide 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 4.0h， 以47%的产率得到methyl α-D-arabino-hexopyranosid-2-ulose
  参考文献：
  名称：

  Catalytic and Regioselective Oxidation of Carbohydrates To Synthesize Keto-Sugars under Mild Conditions

  摘要：

  A new catalytic and regioselective approach for the synthesis of keto-sugars is described. An organotin catalyst, Oc2SnCl2, in the presence of trimethylphenylammonium tribromide ([TMPhA](+)Br3(-)) accelerates the regioselective oxidation at the "axial"-OH group of 1,2-diol moieties in galactopyranosides. The reaction conditions can also be used for the regioselective oxidation of various carbohydrates.

  DOI：

  10.1021/ol502344h

文献信息

• Regioselective mono-oxidation of non-protected glycosides by the bis-tributyltin oxide-bromine method.
  作者：Yoshisuke Tsuda、Naohisa Matsuhira、Kimihiro (Yoshimoto) Kanemitsu

  DOI：10.1248/cpb.33.4095

  日期：——

  Treatment of methyl glycosides with an excess of bis-tributyltin oxide and molecular sieves 3A in chloroform followed by brominolysis resulted in monooxidation to yield oxo-glycosides regioselectively. Thus Me β-D-Glc and Me β-D-Xyl gave the 3-oxo derivatives in more than 90% yield, and Me α-D-Glc, Me α-D-Gal, Me α-D-Xyl, and Me β-L-Ara gave the 4-oxo derivatives in 70-80% yield.

  甲基糖苷与过量的二三丁基锡氧化物和分子筛3A在氯仿中反应，随后进行溴解反应，可以区域选择性地单氧化生成氧代糖苷。因此，Me β-D-葡糖苷和Me β-D-木糖苷以超过90%的产率得到3-氧代衍生物，而Me α-D-葡糖苷、Me α-D-半乳糖苷、Me α-D-木糖苷和Me β-L-阿拉伯糖苷以70-80%的产率得到4-氧代衍生物。
• Utilization of Sugars in Organic Synthesis; Part XXVII. Chemistry of Oxo-Sugars. (2). Regio- and Stereo-Selective Synthesis of Methyl D-Hexopyranosiduloses and Identification of Their Forms Existing in Solutions.
  作者：Hong-Min LIU、Yoshiyuki SATO、Yoshisuke TSUDA

  DOI：10.1248/cpb.41.491

  日期：——

  Sixteen oxo derivatives of methyl D-hexopyranosides with various regio- and stereo-chemistries were selectively synthesized by direct oxidation of non-protected methyl glycosides by the bistributyltin oxide-bromine method or by oxidation of pfrtially protected glycosides followed by deprotection. The forms of these oxoglycosides existing in pryidine-d5 and in H2O (D2O) were investigated by means of 13C-NMR spectroscopy, and it was found that interconversion between oxo and hydrate forms of oxoglycosides readily takes place.

  通过双二丁基氧化锡-溴法直接氧化未受保护的甲基糖苷，或先氧化受部分保护的糖苷再进行脱保护，选择性地合成了十六种具有不同区域和立体化学结构的甲基 D-吡喃己苷的氧化衍生物。通过 13C-NMR 光谱法研究了这些氧化糖苷在 Pryidine-d5 和 H2O（D2O）中的存在形式，发现氧化糖苷的氧化形式和水合物形式之间很容易发生相互转化。
• Utilization of Sugars in Organic Synthesis. Part XXVI. Chemistry of Oxo-Sugars (1). Rearrangement of 2-Oxoglycosides in Pyridine: Evidence of Intramolecular Hydride Shift.
  作者：Yoshisuke TSUDA、Hong-Min LIU

  DOI：10.1248/cpb.40.1975

  日期：——

  Methyl α- and β-D-arabinohexopyranosid-2-uloses rearranged, in pyridine, into methyl α- and β-D-ribo-hexopyranosid-3-uloses through intermediacy of methyl α- and β-D-arabinohexopyranosid-3-uloses, respectively, indicating that an intramolecular hydride shift is the initial reaction for rearrangement of 2-oxoglycosides.

  甲基 α- 和 β-D-arabinoxopyranosid-2-uloses 在吡啶中分别通过中间体甲基 α- 和 β-D-arabinoxopyranosid-3-uloses 重排为甲基 α- 和 β-D-ribo-hexopyranosid-3-uloses ，这表明分子内氢化物转移是 2-氧代糖苷重排的初始反应。
• Utilization of Sugars in Organic Synthesis. XXVIII. Chemistry of Oxo-Sugars. III. Transformations of 2- and 3-Oxoglycosides in a Pyridine Solution.
  作者：Hong-Min LIU、Yoshisuke TSUDA

  DOI：10.1248/cpb.44.80

  日期：——

  Methyl arabino-hexopyranosid-2-uloses rearranged, in pyridine, into arabino-hexopyranosid-3-uloses through an intramolecular hydride shift. The product further isomerized, through enolization, to the most stable ribo-hexopyranosid-3-uloses, which, on prolonged standing in the same solvent, gradually liberated methanol giving rise to dioxo derivatives. The last change was particularly evident for 3-oxoglycosides carrying a 4-axial hydroxyl group.

  甲基阿拉伯糖-吡喃己糖苷-2-吡喃糖在吡啶中通过分子内氢化转移重排为阿拉伯糖-吡喃己糖苷-3-吡喃糖。产物通过烯醇化进一步异构化为最稳定的核糖-吡喃己糖苷-3-吡喃糖，后者在相同的溶剂中长时间放置后，逐渐释放出甲醇，形成二氧代衍生物。对于带有4轴羟基的3-氧代糖苷，最后的变化尤为明显。
• Tsuda, Yoshisuke; Hanajima, Makiko; Matsuhira, Naohisa, Chemical and pharmaceutical bulletin, 1989, vol. 37, # 9, p. 2344 - 2350
  作者：Tsuda, Yoshisuke、Hanajima, Makiko、Matsuhira, Naohisa、Okuno, Yukihiro、Kanemitsu, Kimihiro

  DOI：——

  日期：——