ethyl (3S,4R)-3-(tert-butyldimethylsiloxy)-4-methyl-5-oxocyclopent-1-enecarboxylate | 918150-60-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: ethyl (3S,4R)-3-(tert-butyldimethylsiloxy)-4-methyl-5-oxocyclopent-1-enecarboxylate
• 英文别名: ethyl (3S,4R)-3-[tert-butyl(dimethyl)silyl]oxy-4-methyl-5-oxocyclopentene-1-carboxylate
• CAS: 918150-60-4
• 化学式: C₁₅H₂₆O₄Si
• 分子量: 298.455
• InChiKey: MFXFUGUJRVKVMC-PWSUYJOCSA-N

物化性质

• 沸点：
  345.9±42.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.09
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl (3S,4R)-3-(tert-butyldimethylsiloxy)-4-methyl-5-oxocyclopent-1-enecarboxylate 、 ((3aS,6S,6aS)-6-isopropenyl-2,2-dimethyl-6,6a-dihydro-3aH-cyclopenta[1,3]dioxol-4-yloxy)trimethylsilane 在 正丁基锂 、 zinc(II) chloride 、 copper diacetate 、 manganese triacetate 、 溶剂黄146 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 、 2,2,2-三氟乙醇 为溶剂， 反应 3.0h， 以509 mg的产率得到ethyl (1S,2R,3aR,5aS,5bS,8aS,9aS,9bR)-1-(tert-butyldimethylsiloxy)-2,7,7-trimethyl-5-methylene-3,9-dioxodecahydro-6,8-dioxacyclopenta[b]-as-indacene-3a-carboxylate
  参考文献：
  名称：

  Dramatic Solvent Effect on the Diastereoselectivity of Michael Addition:  Study toward the Synthesis of the ABC Ring System of Hexacyclinic Acid

  摘要：

  During our studies toward the synthesis of the ABC ring system of hexacyclinic acid, we have observed a dramatic influence of the solvent on both our key steps. The diastereoselectivity of the intermolecular Michael addition could be totally reversed by changing the polarity of the solvent, and trifluoroethanol was found to be the optimal solvent for the following Mn(III)-promoted radical cyclization.

  DOI：

  10.1021/ol702566c
• 作为产物：
  描述：

  ethyl (4R,5S)-5-(tert-butyldimethylsiloxy)-4-methyl-3-oxohept-6-enoate 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 吡啶 、 四氯化钛 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 ethyl (3S,4R)-3-(tert-butyldimethylsiloxy)-4-methyl-5-oxocyclopent-1-enecarboxylate
  参考文献：
  名称：

  α-EWG-Substituted Enones: Suitable Substrates for Ring-Closing Metathesis

  摘要：

  己环酸的A环已通过涉及α-吸电子基团取代的烯酮作为关键步骤的环合复分解反应合成。随后，我们探索了该反应的范围，能够获得各种五元和六元环。

  DOI：

  10.1055/s-2006-950274

文献信息

• α-EWG-Substituted Enones: Suitable Substrates for Ring-Closing Metathesis
  作者：Julie Toueg、Joëlle Prunet

  DOI：10.1055/s-2006-950274

  日期：2006.10

  The A-ring of hexacyclinic acid has been synthesised, using a ring-closing metathesis involving an α-EWG-substituted enone as the key step. We have then explored the scope of this reaction, which gives access to various 5- and 6-membered rings.

  己环酸的A环已通过涉及α-吸电子基团取代的烯酮作为关键步骤的环合复分解反应合成。随后，我们探索了该反应的范围，能够获得各种五元和六元环。
• Dramatic Solvent Effect on the Diastereoselectivity of Michael Addition:  Study toward the Synthesis of the ABC Ring System of Hexacyclinic Acid
  作者：Julie Toueg、Joëlle Prunet

  DOI：10.1021/ol702566c

  日期：2008.1.1

  During our studies toward the synthesis of the ABC ring system of hexacyclinic acid, we have observed a dramatic influence of the solvent on both our key steps. The diastereoselectivity of the intermolecular Michael addition could be totally reversed by changing the polarity of the solvent, and trifluoroethanol was found to be the optimal solvent for the following Mn(III)-promoted radical cyclization.