1,5,5-trimethyl-2-methoxycarbonyl-5,6,7,8-tetrahydronaphthalene

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1,5,5-trimethyl-2-methoxycarbonyl-5,6,7,8-tetrahydronaphthalene
• 英文别名: methyl 1,5,5-trimethyl-7,8-dihydro-6H-naphthalene-2-carboxylate
• 化学式: C₁₅H₂₀O₂
• 分子量: 232.323
• InChiKey: JRXPDAVQVQUJNM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  (1E)-2-(6',6'-dimethylcyclohex-1'-enyl)-N,N-dimethylethen-1-ylamine 、 2-丁炔酸甲酯 在 silica gel 作用下， 生成 1,5,5-trimethyl-2-methoxycarbonyl-5,6,7,8-tetrahydronaphthalene
  参考文献：
  名称：

  Total Synthesis of Aegyptinones A and B

  摘要：

  This paper describes the first total syntheses of the diterpene quinones aegyptinones A and B via an extremely direct route which should easily accommodate the production of gram quantities of each compound. The key step in the synthetic strategy involves the application of a recently developed ''second-generation'' photochemical aromatic annulation method for the construction of highly substituted aromatic systems. The synthesis of one of the annulation components, the diazo ketone 5, was achieved using a Diels-Alder-based benzannulation strategy employing cyanoallene and the dienamine 13. Cyanoallene proved to be uniquely effective for this cycloaddition, which either failed or proceeded in poor yield using several substituted acetylenes as dienophiles. The pivotal aromatic annulation reaction was accomplished by irradiating a solution of the diazo ketone 5 and the readily available siloxyalkyne 4 in a Pyrex vessel with a 450-W medium-pressure Hanovia lamp at room temperature for 17-20 h. The desired tricyclic phenol 3 was produced in 58-70% yield and was then converted to aegyptinone B (2) by treatment with tetra-n-butylammonium fluoride in the presence of oxygen. Finally, cyclization to generate aegyptinone A was accomplished in high yield by brief exposure of 2 to an ethanolic solution of concentrated sulfuric acid at room temperature. Overall, this strategy provides efficient routes (six and seven steps, respectively) to aegyptinones A and B which should facilitate the systematic investigation of the pharmacological activity of these novel diterpenes.

  DOI：

  10.1021/jo00096a027

文献信息

• Side-chain migration reactions and ring B aromatization in labdanes: scope and limitations. Synthesis of isofregenedane type tetrahydronaphthalenic diterpenes
  作者：I.S Marcos、P Basabe、M Laderas、D Dı́ez、A Jorge、J.M Rodilla、R.F Moro、A.M Lithgow、I.G Barata、J.G Urones

  DOI：10.1016/s0040-4020(03)00247-3

  日期：2003.3

  The reaction of bicyclic diterpenes with an allylic oxygenated function or an equivalent functionality on ring B in the presence of I2/benzene afforded a simple and rapid synthesis of tetrahydronaphthalenic diterpenes of the isofregenedane class.

  在I 2 /苯存在下，具有环烯丙基氧化官能团或等效官能团的双环二萜在I 2 /苯存在下的反应，可以简单，快速地合成异氟烯烷类的四氢萘二萜。
• Total Synthesis of Aegyptinones A and B
  作者：Rick L. Danheiser、David S. Casebier、Alexandre H. Huboux

  DOI：10.1021/jo00096a027

  日期：1994.8

  This paper describes the first total syntheses of the diterpene quinones aegyptinones A and B via an extremely direct route which should easily accommodate the production of gram quantities of each compound. The key step in the synthetic strategy involves the application of a recently developed ''second-generation'' photochemical aromatic annulation method for the construction of highly substituted aromatic systems. The synthesis of one of the annulation components, the diazo ketone 5, was achieved using a Diels-Alder-based benzannulation strategy employing cyanoallene and the dienamine 13. Cyanoallene proved to be uniquely effective for this cycloaddition, which either failed or proceeded in poor yield using several substituted acetylenes as dienophiles. The pivotal aromatic annulation reaction was accomplished by irradiating a solution of the diazo ketone 5 and the readily available siloxyalkyne 4 in a Pyrex vessel with a 450-W medium-pressure Hanovia lamp at room temperature for 17-20 h. The desired tricyclic phenol 3 was produced in 58-70% yield and was then converted to aegyptinone B (2) by treatment with tetra-n-butylammonium fluoride in the presence of oxygen. Finally, cyclization to generate aegyptinone A was accomplished in high yield by brief exposure of 2 to an ethanolic solution of concentrated sulfuric acid at room temperature. Overall, this strategy provides efficient routes (six and seven steps, respectively) to aegyptinones A and B which should facilitate the systematic investigation of the pharmacological activity of these novel diterpenes.