(4aα,8α,8aα)-(+/-)-octahydro-8-hydroxy-4a,8-dimethyl-2(1H)-naphthalenone | 136391-47-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4aα,8α,8aα)-(+/-)-octahydro-8-hydroxy-4a,8-dimethyl-2(1H)-naphthalenone
• 英文别名: (4aR,8S,8aS)-8-hydroxy-4a,8-dimethyl-3,4,5,6,7,8a-hexahydro-1H-naphthalen-2-one
• CAS: 136391-47-4
• 化学式: C₁₂H₂₀O₂
• 分子量: 196.29
• InChiKey: MXEVPBYXRSDNCO-TUAOUCFPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4aα,8α,8aα)-(+/-)-octahydro-8-hydroxy-4a,8-dimethyl-2(1H)-naphthalenone 在 sodium hydroxide 、 硼烷四氢呋喃络合物 、 双氧水 作用下， 以 二甲基亚砜 为溶剂， 反应 53.0h， 生成 (1S,4aR,8aS)-7-(1-Hydroxy-ethyl)-1,4a-dimethyl-decahydro-naphthalen-1-ol
  参考文献：
  名称：

  Synthesis of all stereoisomers of eudesm-11-en-4-ol. 2. Total synthesis of selin-11-en-4.alpha.-ol, intermedeol, neointermedeol, and paradisiol. First total synthesis of amiteol

  摘要：

  The syntheses of (+/-)-selin-11-en-4-alpha-ol (5), (+/-)-intermedeol (6), (+/-)-neointermedeol (7), (+/-)-amiteol (9), and the four remaining unnatural stereoisomers (+/-)-paradisiol (8), (+/-)-7-epi-amiteol (10), (+/-)-5-epi-neointermedeol (11), and (+/-)-5-epi-paradisiol (12) are described. In addition, the related (+/-)-evuncifer ether (25) has been prepared. The syntheses started from the octahydro-8-hydroxy-4a,8-dimethyl-2(1H)-naphthalenones 1-4. The reaction sequence employed for the synthesis of 5, 7, 9, and 12 involved Wittig reaction, oxidative hydroboration, oxidation, equilibration, and olefination. For the synthesis of 6, 8, 10, and 11 the interim equilibration step was omitted. The oxidative hydroboration was the key step in these syntheses.

  DOI：

  10.1021/jo00026a012
• 作为产物：
  描述：

  (4aα,8aα)-(+/-)-octahydro-7,7-dimethoxy-4a-methyl-1(2H)-napthalenone 在 盐酸 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 反应 1.25h， 生成 (4aα,8α,8aα)-(+/-)-octahydro-8-hydroxy-4a,8-dimethyl-2(1H)-naphthalenone
  参考文献：
  名称：

  Synthesis of all stereoisomers of eudesm-11-en-4-ol. 1. Stereospecific synthesis of the trans- and cis-fused octahydro-8-hydroxy-4a,8-dimethyl-2(1H)-naphthalenones. Conformational analysis of the cis-fused compounds

  摘要：

  An efficient method has been developed for the synthesis of the octahydro-8-hydroxy-4a,8-dimethyl-2-(1H)-naphthalenones 9a-d, which are suitable intermediates in the total synthesis of trans- and cis-fused 1-hydroxyeudesmane sesquiterpenes. Starting from the trans-fused dione 7 the corresponding hydroxy ketones 9a and b could be easily prepared. The cis-fused hydroxy ketones 9c and d were synthesized starting from the dione 8. Protection of the C(7) carbonyl function of 8 as its dimethyl acetal followed by treatment with CH3Li gave the hydroxy ketone 9c. On the other hand, protection of the C(7) carbonyl function of 8 as its ethylene acetal and subsequent treatment with CH3MgI afforded the hydroxy ketone 9d as the main product. NMR studies revealed that 9c exists predominantly in the steroid conformation and that 9d exists exclusively in the nonsteroid conformation.

  DOI：

  10.1021/jo00026a011

文献信息

• Synthesis of all stereoisomers of eudesm-11-en-4-ol. 2. Total synthesis of selin-11-en-4.alpha.-ol, intermedeol, neointermedeol, and paradisiol. First total synthesis of amiteol
  作者：Ronald P. W. Kesselmans、Joannes B. P. A. Wijnberg、Adriaan J. Minnaard、Robert E. Walinga、Aede De Groot

  DOI：10.1021/jo00026a012

  日期：1991.12

  The syntheses of (+/-)-selin-11-en-4-alpha-ol (5), (+/-)-intermedeol (6), (+/-)-neointermedeol (7), (+/-)-amiteol (9), and the four remaining unnatural stereoisomers (+/-)-paradisiol (8), (+/-)-7-epi-amiteol (10), (+/-)-5-epi-neointermedeol (11), and (+/-)-5-epi-paradisiol (12) are described. In addition, the related (+/-)-evuncifer ether (25) has been prepared. The syntheses started from the octahydro-8-hydroxy-4a,8-dimethyl-2(1H)-naphthalenones 1-4. The reaction sequence employed for the synthesis of 5, 7, 9, and 12 involved Wittig reaction, oxidative hydroboration, oxidation, equilibration, and olefination. For the synthesis of 6, 8, 10, and 11 the interim equilibration step was omitted. The oxidative hydroboration was the key step in these syntheses.
• Synthesis of all stereoisomers of eudesm-11-en-4-ol. 1. Stereospecific synthesis of the trans- and cis-fused octahydro-8-hydroxy-4a,8-dimethyl-2(1H)-naphthalenones. Conformational analysis of the cis-fused compounds
  作者：Ronald P. W. Kesselmans、Joannes B. P. A. Wijnberg、Aede De Groot、Nanne K. De Vries

  DOI：10.1021/jo00026a011

  日期：1991.12

  An efficient method has been developed for the synthesis of the octahydro-8-hydroxy-4a,8-dimethyl-2-(1H)-naphthalenones 9a-d, which are suitable intermediates in the total synthesis of trans- and cis-fused 1-hydroxyeudesmane sesquiterpenes. Starting from the trans-fused dione 7 the corresponding hydroxy ketones 9a and b could be easily prepared. The cis-fused hydroxy ketones 9c and d were synthesized starting from the dione 8. Protection of the C(7) carbonyl function of 8 as its dimethyl acetal followed by treatment with CH3Li gave the hydroxy ketone 9c. On the other hand, protection of the C(7) carbonyl function of 8 as its ethylene acetal and subsequent treatment with CH3MgI afforded the hydroxy ketone 9d as the main product. NMR studies revealed that 9c exists predominantly in the steroid conformation and that 9d exists exclusively in the nonsteroid conformation.