异-异绒白乳菇醛 | 109956-89-0

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 中文名称: 异-异绒白乳菇醛
• 英文名称: iso-isovelleral
• 英文别名: <1aR-(2aα,3aα,6aα,6bα)>-3a,4,5,6,6a,6b-hexahydro-5,5,6b-trimethylcyclopropindene-1a,2(1H)-dicarboxaldehyde；Isovelleral；(1aR,3aS,6aS,6bS)-5,5,6b-trimethyl-3a,4,6,6a-tetrahydro-1H-cyclopropa[e]indene-1a,2-dicarbaldehyde
• CAS: 109956-89-0
• 化学式: C₁₅H₂₀O₂
• 分子量: 232.323
• InChiKey: PJAAESPGJOSQGZ-WCUVEOEZSA-N

物化性质

• 沸点：
  322.8±35.0 °C(Predicted)
• 密度：
  1.211±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  异-异绒白乳菇醛 在 重水 作用下， 以 氘代甲苯 、 甲苯 为溶剂， 反应 1.0h， 生成 <12-2H3>-isovelleral
  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：

  (1aS,1bS,4aR,5S,5aS,5bR,8aS,9S,9aS)-1a,3,3,7,7-pentamethyldodecahydrocyclopropa[3a,4]-s-indaceno[1,2-d][1,3]dioxole-5,9-diol 在 吡啶 、 4-二甲氨基吡啶 、 sodium periodate 、 硫酸 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 22.0h， 生成 异-异绒白乳菇醛
  参考文献：
  名称：

  （+）-isovelleral的全合成。蔷薇科倍半萜的绝对构型

  摘要：

  （+）-Isovelleral是来自担子菌的抗生素和拒食性倍半萜烯二醛，它是通过非对映选择性分子内Diels-Alder环化衍生自D-核糖内酯的手性中间体而合成的。

  DOI：

  10.1039/c39900000865

文献信息

• Structure-activity relationships for unsaturated dialdehydes 12. The reactivity of unsaturated dialdehydes towards triacetic acid lactone
  作者：Mikaei Jonassohn、Olov Sterner、Heidrun Anke

  DOI：10.1016/0040-4020(95)00973-6

  日期：1996.1

  triketide triacetic acid lactone (5), forming pentacyclic pyranone adducts. In buffered water solutions, the reaction rates of merulidial (1) and its less active isomer 2 are strongly correlated with the antibiotic activity of the two, suggesting that their electrophilicity as Michael acceptors is important for this activity. The adduct 7, formed between merulidial and triacetic acid lactone, is identical

  真菌抗生素倍他乐醛（1）和异黄酮（3）与天然三酮三乙酸内酯（5）发生立体选择性反应，形成五环吡喃酮加合物。在缓冲水溶液中，髓鞘醛（1）及其活性较低的异构体2的反应速率与二者的抗生素活性密切相关，这表明它们作为迈克尔受体的亲电性对该活性很重要。在甲乙醛酸与三乙酸内酯之间形成的加合物7与先前从真菌木霉菌的培养滤液中分离出的化合物相同。
• The mechanism of the thermal rearrangement of the marasmane sesquiterpene (+)-isovelleral. Cyclopropane ring closure via an intramolecular ene reaction
  作者：Thomas Hansson、Rolf Bergman、Olov Sterner、B�rje Wickberg

  DOI：10.1039/c39900001260

  日期：——

  The reversible thermal conversion of the fungal sesquiterpene Isovelleral (2) into (1) is a unique Intramolecular ene reaction proceeding via the bicyclic enol (3), which is demonstrated by kinetic studies, deuterium incorporation, and the trapping of (3).

  真菌倍半萜异戊二醛（2）到（1）的可逆热转化是通过双环烯醇（3）进行的独特的分子内烯反应，这通过动力学研究，氘掺入和（3）的俘获得以证明。
• Correlation of the reactivity of 1,4-dialdehydes with methylamine in biomimetic conditions to their hot taste: Covalent binding to primary amines as a molecular mechanism in hot taste receptors
  作者：G. Cimino、G. Sodano、A. Spinella

  DOI：10.1016/s0040-4020(01)87721-8

  日期：1987.1
• A total synthesis of (+)-isovelleral. The absolute configuration of the russulaceae sesquiterpenes
  作者：R. Bergman、T. Hansson、O. Sterner、B. Wickberg

  DOI：10.1039/c39900000865

  日期：——

  (+)-Isovelleral, an antibiotic and antifeedant sesquiterpene dialdehyde from Basidiomycetes, has been synthesised via a diastereoselective intramolecular Diels–Alder cyclisation of a chiral intermediate derived from D-ribonolactone.

  （+）-Isovelleral是来自担子菌的抗生素和拒食性倍半萜烯二醛，它是通过非对映选择性分子内Diels-Alder环化衍生自D-核糖内酯的手性中间体而合成的。
• 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.