乙酰基干朽菌醛 | 108893-54-5

• 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
• 中文名称: 乙酰基干朽菌醛
• 英文名称: O-acetylmerulidial
• 英文别名: acetylmerulidial；[(1aR,5aR,6S,6aR)-1a,2-diformyl-4,4,6a-trimethyl-3,5,5a,6-tetrahydro-1H-cyclopropa[f]inden-6-yl] acetate
• CAS: 108893-54-5
• 化学式: C₁₇H₂₂O₄
• 分子量: 290.359
• InChiKey: MJXHKPSYLUUZDJ-QCPWZWHMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  60.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  乙酰基干朽菌醛 在 三乙胺 作用下， 以 甲苯 为溶剂， 反应 9.0h， 生成 <8S-(5ξ,8β,8aβ)>-8-acetoxy-1,2,3,5,6,7,8,8a-octahydro-2,2-dimethyl-7-methylene-4,5-azulenedicarboxaldehyde
  参考文献：
  名称：

  The thermal isomerization of the sesquiterpenes isovelleral and merulidial. A reversible ring opening of the cis-methylcyclopropanecarboxaldehyde group via an intramolecular ene reaction.

  摘要：

  Fungal sesquiterpene dialdehydes of marasmane and isolactarane types, such as isovelleral (1) and merulidial (7), undergo a reversible thermal rearrangement to products (e.g., 2 and 8) with inverted orientations of the cyclopropane rings. The process is shown to involve an intramolecular ene reaction with a bicyclic enol intermediate 13 which was trapped as an E-silyl ether 17. In the presence of D2O, deuterium is incorporated quantitatively into the C-12 methyl groups of 1 and 2. A high kinetic isotope effect is observed for the rearrangement of 1 and its deuterated analogue 24, and the reaction parameters are comparable to those reported for the thermal ring-opening reactions of cis-alkylvinylcyclopropanes and cis-alkyl cyclopropyl ketones. In the presence of weak acid or base, an equilibrium is established between 1, 2, and the hydroazulenic dialdehydes 14 and 15. Dialdehyde 7 reacts less cleanly and incorporates deuterium not only at C-13 but also at C-1 (26). The latter process presumably involves enolization via a [1,5] sigmatropic hydrogen shift.

  DOI：

  10.1021/jo00040a020
• 作为产物：
  描述：

  <8S-(5ξ,8β,8aβ)>-8-acetoxy-1,2,3,5,6,7,8,8a-octahydro-2,2-dimethyl-7-methylene-4,5-azulenedicarboxaldehyde 以 甲苯 为溶剂， 反应 6.0h， 生成 乙酰基干朽菌醛
  参考文献：
  名称：

  The thermal isomerization of the sesquiterpenes isovelleral and merulidial. A reversible ring opening of the cis-methylcyclopropanecarboxaldehyde group via an intramolecular ene reaction.

  摘要：

  Fungal sesquiterpene dialdehydes of marasmane and isolactarane types, such as isovelleral (1) and merulidial (7), undergo a reversible thermal rearrangement to products (e.g., 2 and 8) with inverted orientations of the cyclopropane rings. The process is shown to involve an intramolecular ene reaction with a bicyclic enol intermediate 13 which was trapped as an E-silyl ether 17. In the presence of D2O, deuterium is incorporated quantitatively into the C-12 methyl groups of 1 and 2. A high kinetic isotope effect is observed for the rearrangement of 1 and its deuterated analogue 24, and the reaction parameters are comparable to those reported for the thermal ring-opening reactions of cis-alkylvinylcyclopropanes and cis-alkyl cyclopropyl ketones. In the presence of weak acid or base, an equilibrium is established between 1, 2, and the hydroazulenic dialdehydes 14 and 15. Dialdehyde 7 reacts less cleanly and incorporates deuterium not only at C-13 but also at C-1 (26). The latter process presumably involves enolization via a [1,5] sigmatropic hydrogen shift.

  DOI：

  10.1021/jo00040a020

文献信息

• STERNER, O.;ANKE, T.;SHELDRICK, W. S.;STEGLICH, W., TETRAHEDRON, 46,(1990) N, C. 2389-2400
  作者：STERNER, O.、ANKE, T.、SHELDRICK, W. S.、STEGLICH, W.

  DOI：——

  日期：——
• Antibiotics from basidiomycetes
  作者：Bruno M. Giannetti、Bert Steffan、Wolfgang Steglch、Wolfram Quack、Timm Anke

  DOI：10.1016/s0040-4020(01)87324-5

  日期：1986.1
• The thermal isomerization of the sesquiterpenes isovelleral and merulidial. A reversible ring opening of the cis-methylcyclopropanecarboxaldehyde group via an intramolecular ene reaction.
  作者：Thomas Hansson、Olov Sterner、Boerje Wickberg、Rolf Bergman

  DOI：10.1021/jo00040a020

  日期：1992.7

  Fungal sesquiterpene dialdehydes of marasmane and isolactarane types, such as isovelleral (1) and merulidial (7), undergo a reversible thermal rearrangement to products (e.g., 2 and 8) with inverted orientations of the cyclopropane rings. The process is shown to involve an intramolecular ene reaction with a bicyclic enol intermediate 13 which was trapped as an E-silyl ether 17. In the presence of D2O, deuterium is incorporated quantitatively into the C-12 methyl groups of 1 and 2. A high kinetic isotope effect is observed for the rearrangement of 1 and its deuterated analogue 24, and the reaction parameters are comparable to those reported for the thermal ring-opening reactions of cis-alkylvinylcyclopropanes and cis-alkyl cyclopropyl ketones. In the presence of weak acid or base, an equilibrium is established between 1, 2, and the hydroazulenic dialdehydes 14 and 15. Dialdehyde 7 reacts less cleanly and incorporates deuterium not only at C-13 but also at C-1 (26). The latter process presumably involves enolization via a [1,5] sigmatropic hydrogen shift.