1-methoxy-8,8-dimethylspiro(endo-tricyclo[5.2.2.0^2,6]undeca-3,10-diene-5-1'-cyclopropan)-9-one | 144488-35-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-methoxy-8,8-dimethylspiro(endo-tricyclo[5.2.2.0^2,6]undeca-3,10-diene-5-1'-cyclopropan)-9-one
• CAS: 144488-35-7
• 化学式: C₁₆H₂₀O₂
• 分子量: 244.334
• InChiKey: KKOBZOIREUUEON-KZTGVZKYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.75
• 重原子数：
  18.0
• 可旋转键数：
  1.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-methoxy-8,8-dimethylspiro(endo-tricyclo[5.2.2.0^2,6]undeca-3,10-diene-5-1'-cyclopropan)-9-one 以 丙酮 为溶剂， 反应 3.0h， 以48%的产率得到3,3-dimethylspiro(tricyclo[6.3.0.0^2,6]undec-9-ene-11-1'-cyclopropane)-4,7-dione
  参考文献：
  名称：

  邻香兰醇作为2-甲氧基环己2,4-二酮的合成等同物：线性稠合的顺式：反式：顺式三环戊烷的新颖合成

  摘要：

  tricyclopentanoids的新颖的和有效的合成通过逆需求π 4S +π 2S环加成和的稠合二环[2.2.2]具有α -烷氧基- β，γ不饱和羰基发色团octenones，描述光化学反应。

  DOI：

  10.1039/c39920001211
• 作为产物：
  描述：

  螺[2.4]庚-4,6-二烯 在 sodium periodate 、 十六烷基三甲基溴化铵 、 sodium hydride 、 氯化铵 、 锌 作用下， 以 1,4-二氧六环 、 二氯甲烷 为溶剂， 反应 18.5h， 生成 1-methoxy-8,8-dimethylspiro(endo-tricyclo[5.2.2.0^2,6]undeca-3,10-diene-5-1'-cyclopropan)-9-one
  参考文献：
  名称：

  Aromatics to Triquinanes. Synthesis and Photoreaction of Tricyclo[5.2.2.0^2,6]undecanes Having an α-Methoxy β,γ-Unsaturated Carbonyl Chromophore:  A Novel, Efficient, and General Route to Linearly Fused Cis:Anti:Cis Tricyclopentanoids

  摘要：

  A novel, general, and stereoselective route for rapid creation of functionalized, linearly fused cis:anti:cis triquinanes from aromatic precursors has been presented. Cycloaddition of 2-methoxy-spiro[cyclohexa-2,4-diene-6-2'oxacyclopropan]one with various dienophiles and the photochemical reaction of appropriately designed tricyclic systems, having an alpha-methoxy beta,gamma-enone chromophore upon triplet (T-3) sensitization, are the key elements of our approach. A new and efficient methodology for the synthesis of endo-annulated bicyclo[2.2.2]octenones having an alpha-methoxy beta,gamma-enone chromophore (23-36) from o-vanillyl alcohol has been reported. The 2-methoxyspiro[cyclo-hexa-2,4-diene-6-2'-oxacyclopropan]one was generated by oxidation of o-vanillyl alcohol and trapped with cyclopentadiene (17), spiroheptadiene (18), and dimethylfulvene (19) to give the adducts 20-22 which were elaborated to a variety of chromophoric systems 23-36. The structure and stereochemistry of the tricyclic chromophoric systems (20-36) has been established through their high-field (300 MHz) H-1 NMR, C-13 NMR, and COSY spectra. Triplet-sensitized photochemical reaction of the chromophoric systems (23, 28-35) has been investigated. The triplet excitation of 28-34 led directly to the formation of functionalized triquinanes (43-48) in a single, stereoselective step. Interestingly, the irradiation of 23 furnished a novel tetracyclic product 40, whereas the irradiation of the substrate 35, having an additional alpha,beta-enone chromophore, gave a highly unusual pentacyclic product 55 as a result of participation of the OCH3 group in the photoreaction.

  DOI：

  10.1021/jo9702296