1-methoxyspiro(endo-tricyclo[5.2.2.0^2,6]undeca-3,10-diene-8-2'-oxacyclopropan)-9-one | 144488-30-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-methoxyspiro(endo-tricyclo[5.2.2.0^2,6]undeca-3,10-diene-8-2'-oxacyclopropan)-9-one
• 英文别名: (1'R,2'R,6'S,7'R)-7'-methoxyspiro[oxirane-2,9'-tricyclo[5.2.2.02,6]undeca-4,10-diene]-8'-one
• CAS: 144488-30-2
• 化学式: C₁₃H₁₄O₃
• 分子量: 218.252
• InChiKey: MZADHLXWGZADFD-FSSLKIHNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-methoxyspiro(endo-tricyclo[5.2.2.0^2,6]undeca-3,10-diene-8-2'-oxacyclopropan)-9-one 在 jones' reagent 、 氯化铵 、 锌 作用下， 以 四氢呋喃 、 甲醇 、 水 、 丙酮 为溶剂， 反应 11.0h， 生成 (3aS,4R,7R,7aS)-7-Methoxy-3a,4,7,7a-tetrahydro-3H-4,7-ethano-inden-8-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
• 作为产物：
  描述：

  2-羟基-3-甲氧基苄醇 在 sodium periodate 、 十六烷基三甲基溴化铵 作用下， 以 氯仿 、 水 为溶剂， 反应 6.0h， 生成 1-methoxyspiro(endo-tricyclo[5.2.2.0^2,6]undeca-3,10-diene-8-2'-oxacyclopropan)-9-one
  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

文献信息

• Photodecarbonylation: A novel photoreaction of rigid β,γ-enones
  作者：Vishwakarma Singh、Beena Thomas、Uday Sharma

  DOI：10.1016/0040-4039(95)00497-z

  日期：1995.5

  A novel, photodecarbonylation upon singlet excitation of beta,gamma-enones having wider synthetic potential is described.