(1aα,3aβ,6aβ,6bα)-(+/-)-3a,4,5,6,6a,6b-hexahydro-5,5,6b-trimethylcyclopropindene-1a,2(1H)-dimethanol | 126872-26-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1aα,3aβ,6aβ,6bα)-(+/-)-3a,4,5,6,6a,6b-hexahydro-5,5,6b-trimethylcyclopropindene-1a,2(1H)-dimethanol
• 英文别名: Cycloprop(E)indene-1a,2(1H)-dimethanol, 3a,4,5,6,6a,6b-hexahydro-5,5,6b-trimethyl-, (1aS,3aS,6aS,6bR)-；[(1aS,3aS,6aS,6bR)-1a-(hydroxymethyl)-5,5,6b-trimethyl-3a,4,6,6a-tetrahydro-1H-cyclopropa[e]inden-2-yl]methanol
• CAS: 126872-26-2
• 化学式: C₁₅H₂₄O₂
• 分子量: 236.354
• InChiKey: PXOZBWDPKXNHFQ-DZGBDDFRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1aα,3aβ,6aβ,6bα)-(+/-)-3a,4,5,6,6a,6b-hexahydro-5,5,6b-trimethylcyclopropindene-1a,2(1H)-dimethanol 在 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以73%的产率得到(1aα,2aβ,3β,3aβ,6bα)-(+/-)-octahydro-5,5,6b-trimethyl-5,6-epoxycyclopropindene-1a,2(1H)-dimethanol
  参考文献：
  名称：

  Total synthesis of some marasmane and lactarane sesquiterpenes.

  摘要：

  A general and efficient synthetic route to the marasmane sesquiterpenes (+/-)-isovelleral (2) and (+/-)-stearoylvelutinal (1b) is described. Total syntheses of two other naturally occurring sesquiterpenes, deconjugated anhydrolactarorufin A (5) and lactarorufin A (6), were achieved using an acid-catalyzed ring expansion of lactone 25. All four syntheses are highly stereoselective and do not require the use of any protecting groups. Finally, the protic acid-catalyzed degradation of velutinal (1a) was investigated in an effort to chemically induce the biologically important conversion of velutinal (1a) to isovelleral (2). The experimental results thus obtained indicate that an enzymatic mechanism for the key transformation of velutinal (1a) into isovelleral (2) is more plausible than one that is acid-catalyzed.

  DOI：

  10.1021/jo00048a036
• 作为产物：
  描述：

  (1aα,3aβ,6aβ,6bα)-(+/-)-methyl 3a,4,5,6,6a,6b-hexahydro-5,5,6b-trimethyl-2<<(trifluoromethyl)sulfonyl>oxy>cyclopropindene-1a(1H)-carboxylate 在 palladium diacetate 二异丁基氢化铝 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 2.5h， 生成 (1aα,3aβ,6aβ,6bα)-(+/-)-3a,4,5,6,6a,6b-hexahydro-5,5,6b-trimethylcyclopropindene-1a,2(1H)-dimethanol
  参考文献：
  名称：

  Total synthesis of some marasmane and lactarane sesquiterpenes.

  摘要：

  A general and efficient synthetic route to the marasmane sesquiterpenes (+/-)-isovelleral (2) and (+/-)-stearoylvelutinal (1b) is described. Total syntheses of two other naturally occurring sesquiterpenes, deconjugated anhydrolactarorufin A (5) and lactarorufin A (6), were achieved using an acid-catalyzed ring expansion of lactone 25. All four syntheses are highly stereoselective and do not require the use of any protecting groups. Finally, the protic acid-catalyzed degradation of velutinal (1a) was investigated in an effort to chemically induce the biologically important conversion of velutinal (1a) to isovelleral (2). The experimental results thus obtained indicate that an enzymatic mechanism for the key transformation of velutinal (1a) into isovelleral (2) is more plausible than one that is acid-catalyzed.

  DOI：

  10.1021/jo00048a036

文献信息

• The preparation and bioactivities of (−)-isovelleral1,2
  作者：Mikael Jonassohn、Rikard Hjertberg、Heidrun Anke、Kim Dekermendjian、Arpad Szallasi、Eckhard Thines、Robin Witt、Olov Sterner

  DOI：10.1016/s0968-0896(97)00055-2

  日期：1997.7

  The resolution of synthetic (+/-)-isovelleral (1), via chromatographic separation of the two diastereomers of the (-)-menthoxyacetic acid diester of the corresponding (+/-)-diol (3), yielded both enantiomers of the bioactive fungal metabolite (+)-isovelleral (1). While the antimicrobial and cytotoxic activities of the two enantiomers are comparable, natural (+)-1 is approximately 10 times more mutagenic towards Ames' tester strain TA98 than (-)-1. The two enantiomers of the cyclopropane ring isomer 2 also possess negligible mutagenicity compared to (+)-1. Both (+)-1 and (-)-1 have the same affinity for the vanilloid receptor, but significant different affinity for the dopamine D1 receptor. (C) 1997 Elsevier Science Ltd.