3,4-di-O-acetyl-2,6-dideoxy-α,β-D-arabino-hexopyranose | 127112-84-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4-di-O-acetyl-2,6-dideoxy-α,β-D-arabino-hexopyranose
• 英文别名: Diacetyl-fucal；[(2R,3R,4R)-3-acetyloxy-6-hydroxy-2-methyloxan-4-yl] acetate
• CAS: 127112-84-9；127112-87-2；132814-68-7；132814-74-5
• 化学式: C₁₀H₁₆O₆
• 分子量: 232.233
• InChiKey: AUHYUSJXUNPACJ-IVGJAXLISA-N

物化性质

• 沸点：
  314.1±42.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.02
• 重原子数：
  16.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  82.06
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  3,4-di-O-acetyl-2,6-dideoxy-α,β-D-arabino-hexopyranose 在 吡啶 、 甲醇 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 sodium azide 、 三氟化硼乙醚 、 仲丁基锂 、 sodium hydride 、 potassium carbonate 、 溶剂黄146 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 环己烷 、 dfm 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 44.0h， 生成 tert-butyl (1R,3R,4S,5R)-4-benzyloxytetrahydro-5-methyl-1-(4'-(dimethylvinylsilyl)furan-1'-yl)-2H-pyran-3-ylmethylcarbamate
  参考文献：
  名称：

  普兰霉素天然产物合成的研究。首次全合成异霉素

  摘要：

  我们报告了复杂C-芳基糖苷异基霉素的首次全合成，这是天然存在的多霉素抗生素基达霉素的差向异构体。该合成具有取代萘和糖基化呋喃之间的高效 Diels-Alder 反应，以形成带有悬垂的 angolosamine C-糖苷的蒽核心。Diels-Alder 反应的区域化学结果是通过使用一次性硅系链连接反应性萘和糖基呋喃来控制的，从而使环加成成为分子内的。芳环的苯并吡喃酮部分通过将官能化的乙烯基酰胺环化到高级蒽酚中间体上而附加。万古胺氨基糖苷由O引入→产生β-异头物的C-糖苷重排。随后的再功能化然后导致异奇霉素。

  DOI：

  10.1016/j.tet.2011.05.117
• 作为产物：
  描述：

  3,4-di-O-acetyl-D-rhamnal 在 水 作用下， 生成 3,4-di-O-acetyl-2,6-dideoxy-α,β-D-arabino-hexopyranose
  参考文献：
  名称：

  普兰霉素天然产物合成的研究。首次全合成异霉素

  摘要：

  我们报告了复杂C-芳基糖苷异基霉素的首次全合成，这是天然存在的多霉素抗生素基达霉素的差向异构体。该合成具有取代萘和糖基化呋喃之间的高效 Diels-Alder 反应，以形成带有悬垂的 angolosamine C-糖苷的蒽核心。Diels-Alder 反应的区域化学结果是通过使用一次性硅系链连接反应性萘和糖基呋喃来控制的，从而使环加成成为分子内的。芳环的苯并吡喃酮部分通过将官能化的乙烯基酰胺环化到高级蒽酚中间体上而附加。万古胺氨基糖苷由O引入→产生β-异头物的C-糖苷重排。随后的再功能化然后导致异奇霉素。

  DOI：

  10.1016/j.tet.2011.05.117

文献信息

• Novel stereocontrolled glycosidations of olivoses using montmorillonite K-10 as an environmentally benign catalyst
  作者：Takaaki Jyojima、Naoki Miyamoto、Yasumasa Ogawa、Shuichi Matsumura、Kazunobu Toshima

  DOI：10.1016/s0040-4039(99)00924-7

  日期：1999.7

  Novel stereocontrolled glycosidations of 3,4-di-O-protected olivoses and alcohols using a heterogeneous and environmentally benign solid acid, montmorillonite K-10, have been developed. The glycosidations of the 3-O-Ac-4-O-TBS-olivose (4) and various alcohols using montmorillonite K-10 in CH2Cl2 at 25 degrees C exclusively gave the corresponding alpha-olivosides in high yields. On the other hand, the corresponding beta-olivosides were predominately obtained by the glycosidations of the 3-O-TBS-4-O-Ac-olivose (5) and various alcohols under similar conditions. (C) 1999 Elsevier Science Ltd. Ail rights reserved.
• Substrate Flexibility of Vicenisaminyltransferase VinC Involved in the Biosynthesis of Vicenistatin
  作者：Atsushi Minami、Tadashi Eguchi

  DOI：10.1021/ja0685250

  日期：2007.4.1

  A glycosyltransferase VinC is involved in the biosynthesis of antitumor beta-glycoside antibiotic vicenistatin. It catalyzes a glycosyl transfer reaction between dTDP-alpha-D-vicenisamine and vicenilactam. Previous identification of its broad substrate specificity toward various glycosyl acceptors enabled us to explore the potential of VinC for glycodiversification. In vitro study of the substrate specificity toward several dTDP-sugars with vicenilactam established that VinC displayed activities with alpha-anomers of several dTDP-2-deoxy-D-sugars such as mycarose, digitoxose, olivose, and 2-deoxyglucose to afford respective beta-glycosides. Notably, beta-anomers of dTDP-2-deoxy-D-sugars also appeared to be accepted by VinC to form alpha-glycosides. Furthermore, VinC is capable of catalyzing glycosyl transfer reactions from both the alpha-anomer and beta-anomer of dTDP-L-mycarose, respectively, into beta-glycoside and alpha-glycoside. These results indicate that VinC is a unique glycosyltransferase possessing broad substrate specificity. The mechanism of this axially oriented glycosidic bond formation from the equatorially oriented dTDP-sugar might be explained by conformational change of dTDP-sugar to a boat conformation during the glycosyl transfer reaction. To apply these features of VinC for glycodiversification, 22 sets of structurally diverse glycosides were constructed using unnatural glycosyl donors and acceptors.