(1S,5S)-(-)-5-Isopropyl-7-methylenespiro<5.4>decan-2-one | 163514-13-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,5S)-(-)-5-Isopropyl-7-methylenespiro<5.4>decan-2-one
• 英文别名: (5S,9S)-9-isopropyl-1-methylenespiro[4.5]decan-6-one；(5S,7S)-4-methylidene-7-propan-2-ylspiro[4.5]decan-10-one
• CAS: 163514-13-4
• 化学式: C₁₄H₂₂O
• 分子量: 206.328
• InChiKey: FIGPKZTYJKSNPU-JSGCOSHPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  15
• 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：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1S,5S)-(-)-5-Isopropyl-7-methylenespiro<5.4>decan-2-one 在 氘代甲醇-d 、 potassium carbonate 作用下， 生成 C₁₄H₂₀⁽²⁾H₂O
  参考文献：
  名称：

  Anti Selective Spirocarbomercuration: Synthesis and Stereochemistry of the Spirobicyclic Sesquiterpenes Spirojatamol and Erythrodiene

  摘要：

  The stereoselectivity of mercuric salt-induced spirocarbannulation reactions of substituted and unsubstituted 2-(4-pentynyl)-1-[(trimethylsilyl)oxy]cyclohexenes has been examined. This intramolecular alkyne carbomercuration reaction has been applied to the first enantioselective syntheses of the natural products erythrodiene and spirojatamol. Treatment of 2-(4-pentynyl)-1-[(trimethylsilyl)oxy]cyclohexene with HgCl2 gave 7(E)-mercuriomethylenespiro[4.5]decan-6-one, the product of anti selective carbomercuration. Similar intramolecular carbomercuration of (S)-4-isopropyl-2-(4-pentynyl)-1-[(trimethylsilyl)oxy]cyclohexene, derived from (S)-(-)-perillyl alcohol, gave diastereomeric axial and equatorial spirocarbannulation products in a 7:3 ratio and high yield. Both C-vinylation products, (1S and 1R,5S,7E)-5-isopropyl-7-mercuriomethylenespiro[5.4]decan-2-one), bear (E)-exocyclic vinyl mercurials. The major (1S,5S)-C-vinylation product was converted into both (-)-erythrodiene and (-)-spirojatamol in one and three steps, respectively. Thus, (-)-erythrodiene, a spirobicyclic sesquiterpene hydrocarbon from the Caribbean gorgonian coral Erythropodium caribaeorum, was synthesized from (S)-(-)-perillyl alcohol in 10 steps and approximately 35% overall yield using the mercuric salt-induced spirocarbannulation reaction as the key step. (-)-Spirojatamol, the enantiomer of the natural product isolated from the Indian plant Nardostachys jatamansi, was similarly prepared from (S)-(-)-perillyl alcohol in 12 steps and ca. 20% overall yield. This work indicates that the absolute configuration of (-)-erythrodiene ((1S,5S)-(-)-5-isopropyl-2,7-dimethylenespiro[5.4]decane) is enantiomeric to the carbon skeleton of (1S,5R,8S)-(+)-spirojatamol, the only other naturally occurring sesquiterpene known to posses the 5-isopropyl-2-methylenespiro[5.4]decane skeleton.

  DOI：

  10.1021/jo00114a027
• 作为产物：
  描述：

  4-异丙基环己酮 在 正丁基锂 、 偶氮二异丁腈 、 (+)-双[(R)-1-苯乙基]胺 、 sodium hydride 、 碳酸氢钠 、 间氯过氧苯甲酸 、 lithium chloride 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 环己烷 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 21.5h， 生成 (1S,5S)-(-)-5-Isopropyl-7-methylenespiro<5.4>decan-2-one
  参考文献：
  名称：

  Highly Diastereoselective Formation of Spirocyclic Compounds via 1,5-Hydrogen Transfer:  A Total Synthesis of (−)-Erythrodiene

  摘要：

  A highly stereoselective synthesis of (-)-erythrodiene starting from 4-isopropylcyclohexanone is described. The key reactions are an asymmetric methoxycarbonylation of the starting ketone and a highly diastereoselective radical cascade involving addition of a phenylthiyl radical to a terminal alkyne followed by a 1,5-hydrogen transfer and a 5-exo-cyclization.

  DOI：

  10.1021/ol051426r

文献信息

• Highly Diastereoselective Formation of Spirocyclic Compounds via 1,5-Hydrogen Transfer:  A Total Synthesis of (−)-Erythrodiene
  作者：Mathilde Lachia、Fabrice Dénès、Florent Beaufils、Philippe Renaud

  DOI：10.1021/ol051426r

  日期：2005.9.1

  A highly stereoselective synthesis of (-)-erythrodiene starting from 4-isopropylcyclohexanone is described. The key reactions are an asymmetric methoxycarbonylation of the starting ketone and a highly diastereoselective radical cascade involving addition of a phenylthiyl radical to a terminal alkyne followed by a 1,5-hydrogen transfer and a 5-exo-cyclization.
• Anti Selective Spirocarbomercuration: Synthesis and Stereochemistry of the Spirobicyclic Sesquiterpenes Spirojatamol and Erythrodiene
  作者：He Huang、Craig J. Forsyth

  DOI：10.1021/jo00114a027

  日期：1995.5

  The stereoselectivity of mercuric salt-induced spirocarbannulation reactions of substituted and unsubstituted 2-(4-pentynyl)-1-[(trimethylsilyl)oxy]cyclohexenes has been examined. This intramolecular alkyne carbomercuration reaction has been applied to the first enantioselective syntheses of the natural products erythrodiene and spirojatamol. Treatment of 2-(4-pentynyl)-1-[(trimethylsilyl)oxy]cyclohexene with HgCl2 gave 7(E)-mercuriomethylenespiro[4.5]decan-6-one, the product of anti selective carbomercuration. Similar intramolecular carbomercuration of (S)-4-isopropyl-2-(4-pentynyl)-1-[(trimethylsilyl)oxy]cyclohexene, derived from (S)-(-)-perillyl alcohol, gave diastereomeric axial and equatorial spirocarbannulation products in a 7:3 ratio and high yield. Both C-vinylation products, (1S and 1R,5S,7E)-5-isopropyl-7-mercuriomethylenespiro[5.4]decan-2-one), bear (E)-exocyclic vinyl mercurials. The major (1S,5S)-C-vinylation product was converted into both (-)-erythrodiene and (-)-spirojatamol in one and three steps, respectively. Thus, (-)-erythrodiene, a spirobicyclic sesquiterpene hydrocarbon from the Caribbean gorgonian coral Erythropodium caribaeorum, was synthesized from (S)-(-)-perillyl alcohol in 10 steps and approximately 35% overall yield using the mercuric salt-induced spirocarbannulation reaction as the key step. (-)-Spirojatamol, the enantiomer of the natural product isolated from the Indian plant Nardostachys jatamansi, was similarly prepared from (S)-(-)-perillyl alcohol in 12 steps and ca. 20% overall yield. This work indicates that the absolute configuration of (-)-erythrodiene ((1S,5S)-(-)-5-isopropyl-2,7-dimethylenespiro[5.4]decane) is enantiomeric to the carbon skeleton of (1S,5R,8S)-(+)-spirojatamol, the only other naturally occurring sesquiterpene known to posses the 5-isopropyl-2-methylenespiro[5.4]decane skeleton.