(-)-(1S,5S,7R)-7-ethyl-5-methyl-6,8-dioxabicyclo[3.2.1]oct-3-en-2-one | 180519-91-9

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: (-)-(1S,5S,7R)-7-ethyl-5-methyl-6,8-dioxabicyclo[3.2.1]oct-3-en-2-one
• 英文别名: (1S,5S,7R)-7-ethyl-5-methyl-6,8-dioxabicyclo[3.2.1]oct-3-en-2-one
• CAS: 180519-91-9
• 化学式: C₉H₁₂O₃
• 分子量: 168.192
• InChiKey: QSZHWQOHULROCA-HLTSFMKQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  (-)-(1S,5S,7R)-7-ethyl-5-methyl-6,8-dioxabicyclo[3.2.1]oct-3-en-2-one 在 palladium 10% on activated carbon 、 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 2.0h， 以80%的产率得到(+)-(1S,5S,7R)-7-ethyl-5-methyl-6,8-dioxabicyclo[3.2.1]octan-2-one
  参考文献：
  名称：

  Organometallic Enantiomeric Scaffolding. A Molybdenum-Mediated Intramolecular Nucleophilic Ketalization−Demetalation Cascade. Total Synthesis of (+)-(1R,2S,5S,7R)-2-Hydroxy-exo-brevicomin

  摘要：

  TpMO(CO)(2)(5-OXO-eta(3)-pyranyl) scaffolds bearing an internal alkoxide undergo a novel intramolecular nucleophilic ketalization reaction. The anionic intermediate is easily demetalated, rapidly providing the 6,8-dioxabicyclo[3.2.1]oct-3-en-2-one framework in moderate to good yields with high enantiopurity. An enantiocontrolled total synthesis of (+)-(1R,2S,5S,7R)-2-hydroxy-exo-brevicomin was accomplished utilizing the reaction sequence.

  DOI：

  10.1021/ol901523g
• 作为产物：
  描述：

  (-)-dicarbonyl[hydridotris(1-pyrazolyl)borato]{(2S,6S)-η-(2,3,4)-6-[(R)-1-hydroxypropyl]-2-methyl-5-oxo-5,6-dihydro-2H-pyran-2-yl}molybdenum 在 sodium hydride 、 nitrosyl hexafluorophosphate 作用下， 以 乙二醇二甲醚 、 mineral oil 为溶剂， 反应 2.58h， 以73%的产率得到(-)-(1S,5S,7R)-7-ethyl-5-methyl-6,8-dioxabicyclo[3.2.1]oct-3-en-2-one
  参考文献：
  名称：

  Organometallic Enantiomeric Scaffolding. A Molybdenum-Mediated Intramolecular Nucleophilic Ketalization−Demetalation Cascade. Total Synthesis of (+)-(1R,2S,5S,7R)-2-Hydroxy-exo-brevicomin

  摘要：

  TpMO(CO)(2)(5-OXO-eta(3)-pyranyl) scaffolds bearing an internal alkoxide undergo a novel intramolecular nucleophilic ketalization reaction. The anionic intermediate is easily demetalated, rapidly providing the 6,8-dioxabicyclo[3.2.1]oct-3-en-2-one framework in moderate to good yields with high enantiopurity. An enantiocontrolled total synthesis of (+)-(1R,2S,5S,7R)-2-hydroxy-exo-brevicomin was accomplished utilizing the reaction sequence.

  DOI：

  10.1021/ol901523g

文献信息

• Scope and Limitations of the Photooxidations of 2-(α-Hydroxyalkyl)furans: Synthesis of 2-Hydroxy-<i>exo</i>-brevicomin
  作者：Dimitris Noutsias、Antonia Kouridaki、Georgios Vassilikogiannakis

  DOI：10.1021/ol200027f

  日期：2011.3.4

  Photooxygenation of 2-(alpha-hydroxyalkyl)furans at 5 degrees C in MeOH followed by in situ reduction affords, in one synthetic operation, 6-hydroxy-3(2H)-pyranones and/or 5-hydroxy-2(5H)-furanones. The relative ratio of the final products is highly dependent on the substitution of the starting furan substrate. Photooxygenation of 2-(alpha,beta-dihydroxyalkyl)furans followed by in situ reduction and ketalization with acid rapidly provides the 6,8-dioxabicyclo[3.2.1]oct-3-en-2-one framework. This new methodology was successfully applied to the synthesis of 2-hydroxy-exo-brevicomin.