methyl (2S,3S,4S,5S,6R)-6-(3-azidopropoxy)-3-[(2R,3S,4S,5S,6S)-6-methoxycarbonyl-5-(4-oxopentanoyloxy)-3,4-bis(phenylmethoxy)oxan-2-yl]oxy-4,5-bis(phenylmethoxy)oxane-2-carboxylate | 914955-20-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (2S,3S,4S,5S,6R)-6-(3-azidopropoxy)-3-[(2R,3S,4S,5S,6S)-6-methoxycarbonyl-5-(4-oxopentanoyloxy)-3,4-bis(phenylmethoxy)oxan-2-yl]oxy-4,5-bis(phenylmethoxy)oxane-2-carboxylate
• CAS: 914955-20-7
• 化学式: C₅₀H₅₇N₃O₁₅
• 分子量: 940.014
• InChiKey: KNBDALMTFYEUCZ-ZSFZNBFJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  68
• 可旋转键数：
  28
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  184
• 氢给体数：
  0
• 氢受体数：
  17

反应信息

• 作为反应物：
  描述：

  methyl (2S,3S,4S,5S,6R)-6-(3-azidopropoxy)-3-[(2R,3S,4S,5S,6S)-6-methoxycarbonyl-5-(4-oxopentanoyloxy)-3,4-bis(phenylmethoxy)oxan-2-yl]oxy-4,5-bis(phenylmethoxy)oxane-2-carboxylate 在 氢氧化钾 、 N-碘代丁二酰亚胺 、 三氟甲磺酸三甲基硅酯 、 一水合肼 作用下， 以 四氢呋喃 、 吡啶 、 二氯甲烷 、 水 、 溶剂黄146 为溶剂， 反应 5.67h， 生成
  参考文献：
  名称：

  Stereocontrolled Synthesis of β-d-Mannuronic Acid Esters:  Synthesis of an Alginate Trisaccharide

  摘要：

  A facile synthesis route toward beta-linked mannuronic acid oligomers using the corresponding 1-thiomannuronic acid esters in combination with the Ph2SO/Tf2O or NIS/TMSOTf reagent combinations is presented. The presence of the remotely attached carboxylic ester sufficiently influences the electronic environment to allow good to excellent beta-selectivities.

  DOI：

  10.1021/ja064787q
• 作为产物：
  描述：

  phenyl 2,3-di-O-benzyl-1-thio-α-D-mannopyranosiduronic acid 在 吡啶 、 N-碘代丁二酰亚胺 、 三氟甲磺酸三甲基硅酯 、 potassium carbonate 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 10.0h， 生成 methyl (2S,3S,4S,5S,6R)-6-(3-azidopropoxy)-3-[(2R,3S,4S,5S,6S)-6-methoxycarbonyl-5-(4-oxopentanoyloxy)-3,4-bis(phenylmethoxy)oxan-2-yl]oxy-4,5-bis(phenylmethoxy)oxane-2-carboxylate
  参考文献：
  名称：

  Stereocontrolled Synthesis of β-d-Mannuronic Acid Esters:  Synthesis of an Alginate Trisaccharide

  摘要：

  A facile synthesis route toward beta-linked mannuronic acid oligomers using the corresponding 1-thiomannuronic acid esters in combination with the Ph2SO/Tf2O or NIS/TMSOTf reagent combinations is presented. The presence of the remotely attached carboxylic ester sufficiently influences the electronic environment to allow good to excellent beta-selectivities.

  DOI：

  10.1021/ja064787q

文献信息

• The Stereodirecting Effect of the Glycosyl C5-Carboxylate Ester: Stereoselective Synthesis of β-Mannuronic Acid Alginates
  作者：Jeroen D. C. Codée、Leendert J. van den Bos、Ana-Rae de Jong、Jasper Dinkelaar、Gerrit Lodder、Herman S. Overkleeft、Gijsbert A van der Marel

  DOI：10.1021/jo8020192

  日期：2009.1.2

  2-cis-mannuronates with excellent stereoselectivity. The potential of the mannuronate ester donors in the formation of the β-mannosidic linkage has been capitalized upon in the construction of a mannuronic acid alginate pentamer using a convergent orthogonal glycosylation strategy.

  甘露糖醛酸酯供体的糖基化高度选择性地进行以产生1，2-顺式连接的产物。基于C5-羧酸酯的远程立体定向作用，我们在此提出了这种与直觉相反的选择性的机械原理，已使用没有C5-羧酸酯以外的环取代基的吡喃糖基尿酸酯来证明。据推测，C 5-羧酸酯优选在草碳en中间体中占据轴向位置，从而比4 H 3构象异构体更倾向于形成3 H 4半椅。对3 H 4的亲核攻击半椅中间体以β的形式出现，为1,2-顺式-甘露糖醛酸酯提供了出色的立体选择性。在利用会聚的正交糖基化策略构建甘露糖醛酸海藻酸酯五聚体中，已经利用了甘露糖酸酯供体在形成β-甘露糖苷键中的潜力。
• Stereocontrolled Synthesis of β-<scp>d</scp>-Mannuronic Acid Esters:  Synthesis of an Alginate Trisaccharide
  作者：Leendert J. van den Bos、Jasper Dinkelaar、Herman S. Overkleeft、Gijsbert A. van der Marel

  DOI：10.1021/ja064787q

  日期：2006.10.1

  A facile synthesis route toward beta-linked mannuronic acid oligomers using the corresponding 1-thiomannuronic acid esters in combination with the Ph2SO/Tf2O or NIS/TMSOTf reagent combinations is presented. The presence of the remotely attached carboxylic ester sufficiently influences the electronic environment to allow good to excellent beta-selectivities.