异干朽菌醛 | 121843-89-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 异干朽菌醛
• 英文名称: Isomerulidial
• 英文别名: (1aS,5aR,6S,6aS)-6-hydroxy-4,4,6a-trimethyl-3,5,5a,6-tetrahydro-1H-cyclopropa[f]indene-1a,2-dicarbaldehyde
• CAS: 121843-89-8
• 化学式: C₁₅H₂₀O₃
• 分子量: 248.322
• InChiKey: NFLNZGQBGCPDMT-DZGBDDFRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  18
• 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：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-羟基-6-甲基-2-吡喃酮 、 异干朽菌醛 以 乙酸乙酯 为溶剂， 反应 92.0h， 以26%的产率得到(5aR,6S,7S,8S,9S)-9-formyl-7-hydroxy-3,8-dimethyl-1-oxo-5a,6-(2,2-dimethyl-propano)-8,9-methano-5a,6,7,8,9-pentahydro-2,5-dioxaanthracene
  参考文献：
  名称：

  不饱和二醛的构效关系12.不饱和二醛对三乙酸内酯的反应性

  摘要：

  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。

  DOI：

  10.1016/0040-4020(95)00973-6
• 作为产物：
  描述：

  (1aR,5aR,6S,6aR)-6-(tert-Butyl-dimethyl-silanyloxy)-4,4,6a-trimethyl-3,4,5,5a,6,6a-hexahydro-1H-cyclopropa[f]indene-1a,2-dicarbaldehyde 在 氢氟酸 作用下， 以 乙腈 、 均三甲苯 为溶剂， 反应 5.0h， 生成 异干朽菌醛
  参考文献：
  名称：

  Structure--Activity Relationships for Unsaturated Dialdehydes. 10. The Generation of Bioactive Products by Autoxidation of Isovelleral and Merulidial.

  摘要：

  The autoxidation of the two mutagenic and antimicrobial sesquiterpenes merulidial (1a) and isovelleral (5) generates a number of bioactive products that are suggested to be partly responsible for the mutagenic and antimicrobial activities of the two compounds. The biological activities of the autoxidation products are, as far as has been possible to assay, of the same order as the parent compounds, and it is shown that they are formed in normal bioassay media. Merulidial (1a) is especially interesting, as its rate of autoxidation is considerably higher compared with non-mutagenic derivatives of 1a. In addition, natural isovelleral [(+)-5] was found to be twice as mutagenic as synthetic isovelleral [(+/-)-5], indicating that (-)-isovelleral is only weakly active or inactive, and supporting the suggestion that the interaction of isovelleral (5) and its derivatives with DNA depends on the absolute stereochemistry of the unsaturated dialdehyde moiety.

  DOI：

  10.3891/acta.chem.scand.49-0530

文献信息

• 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.
• 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。
• Structure--Activity Relationships for Unsaturated Dialdehydes. 10. The Generation of Bioactive Products by Autoxidation of Isovelleral and Merulidial.
  作者：Mikael Jonassohn、Heidrun Anke、Paloma Morales、Olov Sterner、Inger Søtofte、Frode Mo、Tamas Bartfai、Ülo Langel

  DOI：10.3891/acta.chem.scand.49-0530

  日期：——

  The autoxidation of the two mutagenic and antimicrobial sesquiterpenes merulidial (1a) and isovelleral (5) generates a number of bioactive products that are suggested to be partly responsible for the mutagenic and antimicrobial activities of the two compounds. The biological activities of the autoxidation products are, as far as has been possible to assay, of the same order as the parent compounds, and it is shown that they are formed in normal bioassay media. Merulidial (1a) is especially interesting, as its rate of autoxidation is considerably higher compared with non-mutagenic derivatives of 1a. In addition, natural isovelleral [(+)-5] was found to be twice as mutagenic as synthetic isovelleral [(+/-)-5], indicating that (-)-isovelleral is only weakly active or inactive, and supporting the suggestion that the interaction of isovelleral (5) and its derivatives with DNA depends on the absolute stereochemistry of the unsaturated dialdehyde moiety.