(pentyne-4 yl)-6 trimethylsiloxy-1 cyclohexene-1 | 94645-08-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (pentyne-4 yl)-6 trimethylsiloxy-1 cyclohexene-1
• 英文别名: 1-<(Trimethylsilyl)oxy>-2-(4-pentynyl)-1-cyclohexene；trimethyl-(2-pent-4-ynylcyclohexen-1-yl)oxysilane
• CAS: 94645-08-6
• 化学式: C₁₄H₂₄OSi
• 分子量: 236.429
• InChiKey: ONFJAFRMPKAGSN-UHFFFAOYSA-N

物化性质

• 沸点：
  273.9±33.0 °C(Predicted)
• 密度：
  0.90±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.47
• 重原子数：
  16.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (pentyne-4 yl)-6 trimethylsiloxy-1 cyclohexene-1 在 diclazuril 、 重水 、 六甲基二硅氮烷 、 sodium iodide 、 mercury dichloride 作用下， 生成 7-(E-Deuteriomethylene)spiro<5.4>decan-2-one
  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：

  2-(pent-4-ynyl)cyclohexanone 、 三甲基氯硅烷 生成 (pentyne-4 yl)-6 trimethylsiloxy-1 cyclohexene-1
  参考文献：
  名称：

  BOAVENTURA, MARIA-AMELIA;DROUIN, JACQUES, BULL. SOC. CHIM. FR.,(1987) N 6, 1015-1026

  摘要：

  DOI：

文献信息

• Boaventura, Maria-Amelia; Drouin, Jacques, Bulletin de la Societe Chimique de France, 1987, # 6, p. 1015 - 1026
  作者：Boaventura, Maria-Amelia、Drouin, Jacques

  DOI：——

  日期：——
• Cyclization of acetylenic carbonyl compounds via their silyl enol ether derivatives: a new intramolecular C-vinylation induced by mercury(II) salts. Stereochemistry and functionalization of the intermediate vinylmercurial
  作者：Jacques Drouin、Maria Amelia Boaventura、Jean Marie Conia

  DOI：10.1021/ja00292a045

  日期：1985.3
• DROUIN, J.;BOAVENTURA, M. -A.;CONIA, J. -M., J. AMER. CHEM. SOC., 1985, 107, N 6, 1726-1729
  作者：DROUIN, J.、BOAVENTURA, M. -A.、CONIA, J. -M.

  DOI：——

  日期：——