(1R*,6R*)-2-Methoxy-3,6,9,9-tetramethylbicyclo<4.2.1>non-2-en-4-one

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 乙烯酯类
• 英文名称: (1R*,6R*)-2-Methoxy-3,6,9,9-tetramethylbicyclo<4.2.1>non-2-en-4-one
• 英文别名: (1R,6R)-5-methoxy-1,4,9,9-tetramethylbicyclo[4.2.1]non-4-en-3-one
• 化学式: C₁₄H₂₂O₂
• 分子量: 222.327
• InChiKey: ZAFHCXKYCVNLEC-IINYFYTJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (1R*,6R*)-6,9,9-Trimethylbicyclo<4.2.1>nonane-2,4-dione 、 碘甲烷 在 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 3.0h， 以36%的产率得到(1R*,6R*)-4-Methoxy-6,9,9-trimethylbicyclo<4.2.1>non-3-en-2-one
  参考文献：
  名称：

  Total Synthesis of (.+-.)-Tetramethylmediterraneol B

  摘要：

  A diterpenoid having the structure proposed for the tetramethylated derivative 2 of mediterraneol B (1) has been synthesized in a stereocontrolled manner via coupling between the hydroquinone side chain 7 and the bicyclo[4.2.1]nonane core 8 followed by buildup of the 1,3-diketone functionality. The hydroquinone segment 7 was prepared easily according to the reported method. Synthesis of the key component 8 was undertaken starting from tert-butylcyclohexenone 11. The cornerstone of the synthesis is the acid-catalyzed rearrangement of bicyclo[4.2.0]octanone 10 to the ketone 9 which has the bicyclononane skeleton and has clues for further manipulation. As a model study for introduction of the 1,3-diketone functionality, bicyclo[4.2.1]nonane-2,4-dione 43 was also prepared. Methylation of the penultimate intermediate 62 under conditions reported in isolation of the natural product did not give the tetramethyl ether 2 but a mixture of the trimethyl ethers 64 and 65. With Me(3)OBF(4) and Proton Sponge, the transformation to 2 was successfully achieved. The structure of the synthetic 2 was secured by the X-ray crystallographic structure analysis of the key compound 60. However, the difference between the spectra of the synthetic 2 and those of the compound derived from the natural product suggests the structure of the latter is incorrect and requires revision.

  DOI：

  10.1021/jo00116a014

文献信息

• Total Synthesis of (.+-.)-Tetramethylmediterraneol B
  作者：Kiyomi Kakiuchi、Ippei Nakamura、Fumiyuki Matsuo、Morio Nakata、Mikihiro Ogura、Yoshito Tobe、Hideo Kurosawa

  DOI：10.1021/jo00116a014

  日期：1995.6

  A diterpenoid having the structure proposed for the tetramethylated derivative 2 of mediterraneol B (1) has been synthesized in a stereocontrolled manner via coupling between the hydroquinone side chain 7 and the bicyclo[4.2.1]nonane core 8 followed by buildup of the 1,3-diketone functionality. The hydroquinone segment 7 was prepared easily according to the reported method. Synthesis of the key component 8 was undertaken starting from tert-butylcyclohexenone 11. The cornerstone of the synthesis is the acid-catalyzed rearrangement of bicyclo[4.2.0]octanone 10 to the ketone 9 which has the bicyclononane skeleton and has clues for further manipulation. As a model study for introduction of the 1,3-diketone functionality, bicyclo[4.2.1]nonane-2,4-dione 43 was also prepared. Methylation of the penultimate intermediate 62 under conditions reported in isolation of the natural product did not give the tetramethyl ether 2 but a mixture of the trimethyl ethers 64 and 65. With Me(3)OBF(4) and Proton Sponge, the transformation to 2 was successfully achieved. The structure of the synthetic 2 was secured by the X-ray crystallographic structure analysis of the key compound 60. However, the difference between the spectra of the synthetic 2 and those of the compound derived from the natural product suggests the structure of the latter is incorrect and requires revision.