(4aα,8β,8aβ)-(+/-)-octahydro-8-hydroxy-4a,8-dimethyl-2(1H)-naphthalenone | 58844-48-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4aα,8β,8aβ)-(+/-)-octahydro-8-hydroxy-4a,8-dimethyl-2(1H)-naphthalenone
• 英文别名: (+/-)-8t-hydroxy-4a,8c-dimethyl-(4ar,8at)-octahydro-naphthalen-2-one；(+/-)-8t-Hydroxy-4a,8c-dimethyl-(4ar,8at)-octahydro-naphthalin-2-on；4-Hydroxy-11,12,13-trinorselinan-7-on；(4aS,8S,8aS)-8-hydroxy-4a,8-dimethyl-3,4,5,6,7,8a-hexahydro-1H-naphthalen-2-one
• CAS: 58844-48-7
• 化学式: C₁₂H₂₀O₂
• 分子量: 196.29
• InChiKey: MXEVPBYXRSDNCO-SRVKXCTJSA-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,8β,8aβ)-(+/-)-octahydro-8-hydroxy-4a,8-dimethyl-2(1H)-naphthalenone 在 亚磷酸 、 高氯酸 、 potassium tert-butylate 、 二异丙胺 、 三氯氧磷 作用下， 反应 6.75h， 生成 (+/-)-(3,4,4a,5,6,7-Hexahydro-4a,8-dimethyl-2-naphthalenyl)-1-ethanone
  参考文献：
  名称：

  Regioselective intramolecular base-Induced synthesis of .alpha.,.beta.-Unsaturated. Acyldecalins from Decalones via Carbon Homologation with isocyanomethyl Tosylate (TosMIC). Synthesis of (.+-.)-6-Eudesmen-4.alpha.-ol and (.+-.)-Vetiselinene

  摘要：

  Reaction of decalones 6a-e with TosMIC gives adducts 7a-e which can be methylated concomitant with regioselective migration of the double bond to an endocyclic position. The regioselectivity of the double bond migration is determined by the presence or absence of a free hydroxyl group at C(4). Base-catalyzed methylation of TosMIC adducts 7b-d, possessing a free hydroxyl group at C(4), and subsequent acid-catalyzed hydrolysis led preferentially to the C(6)-C(7) double bond isomers 10b-d, respectively. An intramolecular deprotonation of H-6 is considered to be responsible for this regioselectivity. If the hydroxyl group at C(4) is absent or protected as in 7a and 7e, respectively, the C(7)-C(8) double bond isomers 9a and 9c are obtained via an intermolecular abstraction of a sterically less shielded proton at C(8). The usefulness of this methodology is illustrated by the total synthesis of (+/-)-6-eudesmen-4 alpha-ol (18) and (+/-)-vetiselinene (22).

  DOI：

  10.1021/jo00112a044
• 作为产物：
  描述：

  (1E,5E)-1,5-二甲基-8-(丙-2-亚基)环癸-1,5-二烯 在 硫酸 作用下， 以 丙酮 为溶剂， 生成 (4aα,8β,8aβ)-(+/-)-octahydro-8-hydroxy-4a,8-dimethyl-2(1H)-naphthalenone
  参考文献：
  名称：

  Brown,E.D. et al., Journal of the Chemical Society. Perkin transactions I, 1975, p. 2326 - 2332

  摘要：

  DOI：

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.
• Motl et al., Collection of Czechoslovak Chemical Communications, 1958, vol. 23, p. 1297,1304
  作者：Motl et al.

  DOI：——

  日期：——
• 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.
• Regioselective intramolecular base-Induced synthesis of .alpha.,.beta.-Unsaturated. Acyldecalins from Decalones via Carbon Homologation with isocyanomethyl Tosylate (TosMIC). Synthesis of (.+-.)-6-Eudesmen-4.alpha.-ol and (.+-.)-Vetiselinene
  作者：Gonzalo Blay、Robert Schrijvers、Joannes B. P. A. Wijnberg、Aede de Groot

  DOI：10.1021/jo00112a044

  日期：1995.4

  Reaction of decalones 6a-e with TosMIC gives adducts 7a-e which can be methylated concomitant with regioselective migration of the double bond to an endocyclic position. The regioselectivity of the double bond migration is determined by the presence or absence of a free hydroxyl group at C(4). Base-catalyzed methylation of TosMIC adducts 7b-d, possessing a free hydroxyl group at C(4), and subsequent acid-catalyzed hydrolysis led preferentially to the C(6)-C(7) double bond isomers 10b-d, respectively. An intramolecular deprotonation of H-6 is considered to be responsible for this regioselectivity. If the hydroxyl group at C(4) is absent or protected as in 7a and 7e, respectively, the C(7)-C(8) double bond isomers 9a and 9c are obtained via an intermolecular abstraction of a sterically less shielded proton at C(8). The usefulness of this methodology is illustrated by the total synthesis of (+/-)-6-eudesmen-4 alpha-ol (18) and (+/-)-vetiselinene (22).
• Brown,E.D. et al., Journal of the Chemical Society. Perkin transactions I, 1975, p. 2326 - 2332
  作者：Brown,E.D. et al.

  DOI：——

  日期：——