(3R)-3-[(8R,9R)-9-methyl-1,4-dioxaspiro[4.4]nonan-8-yl]butanal | 141245-37-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3R)-3-[(8R,9R)-9-methyl-1,4-dioxaspiro[4.4]nonan-8-yl]butanal
• CAS: 141245-37-6
• 化学式: C₁₂H₂₀O₃
• 分子量: 212.289
• InChiKey: WQJRZLRWHLLEAD-GMTAPVOTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3R)-3-[(8R,9R)-9-methyl-1,4-dioxaspiro[4.4]nonan-8-yl]butanal 在 palladium on activated charcoal 盐酸 、 氢气 作用下， 以 甲醇 、 乙醇 、 水 为溶剂， 生成 (2RS,3RS)-2-methyl-3-<(1RS)-1,5-dimethylhexyl>cyclopentanone
  参考文献：
  名称：

  Asymmetric synthese of de-ABC-cholestan-14-one and de-AB-cholest-8-en-9-one by an extracyclic methodology

  摘要：

  Efficient asymmetric syntheses of the title compounds have been performed starting from a cyclopentanone derivative which was obtained both diastereo- and enantio-selectively by the addition reaction of (S)-2-(8-phenylmenthoxycarbonyl)-2-cyclopentenone with E-methyldiphenylcrotylsilane.

  DOI：

  10.1016/s0040-4039(00)91650-2
• 作为产物：
  描述：

  4-((tert-butyldimethylsilyl)oxy)-2-methylbutan-1-ol 在 palladium on activated charcoal 正丁基锂 、 草酰氯 、 三氟化硼乙醚 、 氢气 、 对甲苯磺酸 、 二甲基亚砜 、 三苯基膦 、 pyridinium chlorochromate 作用下， 以 乙醇 、 二氯甲烷 、 苯 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 22.0h， 生成 (3R)-3-[(8R,9R)-9-methyl-1,4-dioxaspiro[4.4]nonan-8-yl]butanal
  参考文献：
  名称：

  Stereoselective Preparation of Vitamin D Precursors Using the Intramolecular Coupling of Alkynes and Cyclopropylcarbene−Chromium Complexes:  A Formal Total Synthesis of (±)-Vitamin D₃

  摘要：

  The intramolecular coupling of alkynes and cyclopropylcarbene-chromium complexes has been examined. Complexes that feature a stereogenic center at the propargylic position of the alkyne-carbene tether are the focus of this paper. The reaction produces a cyclopentadienone intermediate fused to an oxygen heterocycle, which is reduced to the corresponding cyclopentenone under the reaction conditions (100 degrees C in aqueous toluene). The preexisting stereogenic center has a powerful influence on the reduction of the cyclopentadienone ring, and predominantly a single diastereomer is produced in the reaction. Reductive cleavage of the heterocyclic ring with retention of stereochemistry affords compounds featuring a stereocenter on the five-membered ring and on a side chain. Use of the above reaction processes for the synthesis of the vitamin D precursor de-ABC-cholestan-14-one is also discussed.

  DOI：

  10.1021/jo972186z

文献信息

• Asymmetric synthese of de-ABC-cholestan-14-one and de-AB-cholest-8-en-9-one by an extracyclic methodology
  作者：Li-Rui Pan、Takashi Tokoroyama

  DOI：10.1016/s0040-4039(00)91650-2

  日期：1992.3

  Efficient asymmetric syntheses of the title compounds have been performed starting from a cyclopentanone derivative which was obtained both diastereo- and enantio-selectively by the addition reaction of (S)-2-(8-phenylmenthoxycarbonyl)-2-cyclopentenone with E-methyldiphenylcrotylsilane.
• Stereoselective Preparation of Vitamin D Precursors Using the Intramolecular Coupling of Alkynes and Cyclopropylcarbene−Chromium Complexes:  A Formal Total Synthesis of (±)-Vitamin D₃
  作者：Jingbo Yan、James W. Herndon

  DOI：10.1021/jo972186z

  日期：1998.4.1

  The intramolecular coupling of alkynes and cyclopropylcarbene-chromium complexes has been examined. Complexes that feature a stereogenic center at the propargylic position of the alkyne-carbene tether are the focus of this paper. The reaction produces a cyclopentadienone intermediate fused to an oxygen heterocycle, which is reduced to the corresponding cyclopentenone under the reaction conditions (100 degrees C in aqueous toluene). The preexisting stereogenic center has a powerful influence on the reduction of the cyclopentadienone ring, and predominantly a single diastereomer is produced in the reaction. Reductive cleavage of the heterocyclic ring with retention of stereochemistry affords compounds featuring a stereocenter on the five-membered ring and on a side chain. Use of the above reaction processes for the synthesis of the vitamin D precursor de-ABC-cholestan-14-one is also discussed.