(4aα,8β,8aβ)-(+/-)-(3,4,4a,5,6,7,8,8a-Octahydro-8-hydroxy-4a,8-dimethyl-2-naphthalenyl)-1-ethanone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4aα,8β,8aβ)-(+/-)-(3,4,4a,5,6,7,8,8a-Octahydro-8-hydroxy-4a,8-dimethyl-2-naphthalenyl)-1-ethanone
• 英文别名: 1-[(4aS,8S,8aS)-8-hydroxy-4a,8-dimethyl-3,4,5,6,7,8a-hexahydronaphthalen-2-yl]ethanone
• 化学式: C₁₄H₂₂O₂
• 分子量: 222.327
• InChiKey: DSEZJLPNUXFNKQ-IHRRRGAJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 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：
  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)-(+/-)-(3,4,4a,5,6,7,8,8a-Octahydro-8-hydroxy-4a,8-dimethyl-2-naphthalenyl)-1-ethanone 在 Wilkinson's catalyst 、 氢气 、 碘 、 magnesium 作用下， 以 甲醇 、 苯 为溶剂， 10.0 ℃ 、199.94 kPa 条件下， 反应 8.5h， 生成 4S,5S,10S-selin-6-en-4-ol
  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：

  (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 (4aα,8β,8aβ)-(+/-)-(3,4,4a,5,6,7,8,8a-Octahydro-8-hydroxy-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

文献信息

• 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).