Methyl (-)-(4S,6R)-2-(equatorial)-hydroxy-4,6-dimethyl-8-oxobicyclo<3.2.1>octane-5-carboxylate | 172341-42-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl (-)-(4S,6R)-2-(equatorial)-hydroxy-4,6-dimethyl-8-oxobicyclo<3.2.1>octane-5-carboxylate
• 英文别名: methyl (1S,2S,4S,5S,7R)-4-hydroxy-2,7-dimethyl-8-oxobicyclo[3.2.1]octane-1-carboxylate
• CAS: 172341-42-3
• 化学式: C₁₂H₁₈O₄
• 分子量: 226.273
• InChiKey: WELSISLRSXNGBR-FJVRFIPSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methyl (-)-(4S,6R)-2-(equatorial)-hydroxy-4,6-dimethyl-8-oxobicyclo<3.2.1>octane-5-carboxylate 在 potassium carbonate 作用下， 反应 6.0h， 生成 Dimethyl cis-4,6-dimethyl-1-cycloheptene-5,5-dicarboxylate
  参考文献：
  名称：

  One-Pot Base-Promoted Tandem Michael Addition-Intramolecular Aldolization. Stereoselective Synthesis and Reactivity of 2-Hydroxybicyclo[3.2.1]octan-8-ones

  摘要：

  alpha-Substituted cyclopentanones 1 react with alpha,beta-unsaturated aldehydes 2 by a facile base-promoted (K2CO3, Cs2CO3, DBU) tandem Michael addition-intramolecular aldol cyclization to give, in synthetically useful yields (30-99%), highly substituted, stereodefined and optically active 2-hydroxybicyclo[3.2.1]octan-8-ones 3-19. A generally separable mixture of isomers, in which the one bearing an equatorial hydroxy group predominates, is obtained with simple aldehydes. In the case of prostereogenic Michael accepters one diastereomer usually prevails from as little as 75% to as much as >97%. This high axial-C-4 stereoselectivity results from a diastereoselective Michael addition and can be easily reversed by simple adaptation of the reaction conditions. The structures of the products rest upon NMR spectroscopy and chemical transformations. The synthetic potential of hydroxybicyclo[3.2.1]octanes is illustrated by transformations of 25-28, especially by their facile conversion to functionalized and stereodefined cycloheptanes 30, 32, 35-42.

  DOI：

  10.1021/jo00126a044
• 作为产物：
  描述：

  巴豆醛 、 methyl (1S,2R)-2-methyl-5-oxocyclopentane-1-carboxylate 在 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 48.0h， 生成 Methyl (4R,6R)-2-(equatorial)-hydroxy-4,6-dimethyl-8-oxobicyclo<3.2.1>octane-5-carboxylate 、 Methyl (-)-(4S,6R)-2-(axial)-hydroxy-4,6-dimethyl-8-oxobicyclo<3.2.1>octane-5-carboxylate 、 Methyl (-)-(4S,6R)-2-(equatorial)-hydroxy-4,6-dimethyl-8-oxobicyclo<3.2.1>octane-5-carboxylate
  参考文献：
  名称：

  One-Pot Base-Promoted Tandem Michael Addition-Intramolecular Aldolization. Stereoselective Synthesis and Reactivity of 2-Hydroxybicyclo[3.2.1]octan-8-ones

  摘要：

  alpha-Substituted cyclopentanones 1 react with alpha,beta-unsaturated aldehydes 2 by a facile base-promoted (K2CO3, Cs2CO3, DBU) tandem Michael addition-intramolecular aldol cyclization to give, in synthetically useful yields (30-99%), highly substituted, stereodefined and optically active 2-hydroxybicyclo[3.2.1]octan-8-ones 3-19. A generally separable mixture of isomers, in which the one bearing an equatorial hydroxy group predominates, is obtained with simple aldehydes. In the case of prostereogenic Michael accepters one diastereomer usually prevails from as little as 75% to as much as >97%. This high axial-C-4 stereoselectivity results from a diastereoselective Michael addition and can be easily reversed by simple adaptation of the reaction conditions. The structures of the products rest upon NMR spectroscopy and chemical transformations. The synthetic potential of hydroxybicyclo[3.2.1]octanes is illustrated by transformations of 25-28, especially by their facile conversion to functionalized and stereodefined cycloheptanes 30, 32, 35-42.

  DOI：

  10.1021/jo00126a044