(1aα,3aβ,6aβ,6bα)-(+/-)-methyl 2-formyl-3a,4,5,6,6a,6b-hexahydro-5,5,6b-trimethyl-1H-cyclopropindene-1a-carboxylate | 143347-42-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (1aα,3aβ,6aβ,6bα)-(+/-)-methyl 2-formyl-3a,4,5,6,6a,6b-hexahydro-5,5,6b-trimethyl-1H-cyclopropindene-1a-carboxylate
• 英文别名: methyl (1aS,3aS,6aS,6bR)-2-formyl-5,5,6b-trimethyl-3a,4,6,6a-tetrahydro-1H-cyclopropa[e]indene-1a-carboxylate
• CAS: 143347-42-6
• 化学式: C₁₆H₂₂O₃
• 分子量: 262.349
• InChiKey: XCZISHWZOBSULG-DUUOMRMWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1aα,3aβ,6aβ,6bα)-(+/-)-methyl 2-formyl-3a,4,5,6,6a,6b-hexahydro-5,5,6b-trimethyl-1H-cyclopropindene-1a-carboxylate 在 sodium tetrahydroborate 、 cerium(III) chloride 、 硫酸 、 二甲基二环氧乙烷 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 水 、 丙酮 为溶剂， 反应 8.5h， 生成 lactarorufin A
  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：

  cis-(+/-)-methyl 2,3,3a,6,7,7a-hexahydro-2,2,4-trimethyl-6-oxo-1H-indene-5-carboxylate 在 四(三苯基膦)钯 三正丁基氢锡 、 lithium chloride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， -78.0~50.0 ℃ 、303.98 kPa 条件下， 反应 24.17h， 生成 (1aα,3aβ,6aβ,6bα)-(+/-)-methyl 2-formyl-3a,4,5,6,6a,6b-hexahydro-5,5,6b-trimethyl-1H-cyclopropindene-1a-carboxylate
  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

• Total synthesis of some marasmane and lactarane sesquiterpenes.
  作者：Scott K. Thompson、Clayton H. Heathcock

  DOI：10.1021/jo00048a036

  日期：1992.10

  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.