(3aα,6α,6aα)-hexahydro-3,3,6-trimethyl-1H-cyclopenta[c]furanon-1-one | 78247-16-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (3aα,6α,6aα)-hexahydro-3,3,6-trimethyl-1H-cyclopenta[c]furanon-1-one
• 英文别名: trans-puleganolide；(1S)-2t-Methyl-5c-(α-hydroxy-isopropyl)-cyclopentan-carbonsaeure-(1r)-lacton；(3aR,6R,6aS)-3,3,6-trimethylhexahydro-1H-cyclopenta[c]furan-1-one；(3aR,6R,6aS)-3,3,6-trimethyl-4,5,6,6a-tetrahydro-3aH-cyclopenta[c]furan-1-one
• CAS: 78247-16-2
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: LIISBTATGMRIML-PRJMDXOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3aα,6α,6aα)-hexahydro-3,3,6-trimethyl-1H-cyclopenta[c]furanon-1-one 在 氢氧化钾 、 sodium hydroxide 、 diisoamyl borane 、 potassium tert-butylate 、 双氧水 、 对甲苯磺酸 、 pyridinium chlorochromate 作用下， 以 乙醚 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 20.0~300.0 ℃ 、133.32 Pa 条件下， 反应 17.25h， 生成 (4aR,7R,7aS)-nepetalactone
  参考文献：
  名称：

  The aphid sex pheromone cyclopentanoids: Synthesis in the elucidation of structure and biosynthetic pathways

  摘要：

  Identification of a range of aphid sex pheromones as comprising the cyclopentanoids (4aS,7S,7aR)-nepetalactune, (1R,4aS,7S,7aR)-nepetalactol and the (1S)- and (1R,4aR,7S,7aS)-nepetalactols required samples authenticated by H-1 and C-13 NMR. These and related compounds were provided by small scale synthesis and extraction from plants in the genus Nepeta (Lamiaceae). The subsequent discovery that the synthetic sex pheromones could attract males, and also parasitic wasps that attack aphids, has created a need for large scale syntheses of the cyclopentanoids. This is afforded by cyclisation of the 8-oxo-1-enamine of citronellal as originally developed by Schreiber and co-workers (1986). Investigation into the biosynthesis of the cyclopentanoids by plants for exploiting aphid sex pheromones in crop protection by means of molecular biology required synthesis of putative biosynthetic intermediates, some with radioactive isotopic labelling, particularly 8-oxidised monoterpene alcohols and aldehydes. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0968-0896(96)00012-0
• 作为产物：
  描述：

  3,7-dimethyl-1,1-bis(methylthio)-1,6-octadiene 在 ammonium cerium(IV) nitrate 作用下， 以 水 、 乙腈 为溶剂， 反应 12.0h， 以41%的产率得到(3aα,6α,6aα)-hexahydro-3,3,6-trimethyl-1H-cyclopenta[c]furanon-1-one
  参考文献：
  名称：

  Oxidative Cyclization of Unsaturated Ketene Dithioacetals with Ceric Ammonium Nitrate to Form Bicyclic Lactones

  摘要：

  Ceric ammonium nitrate oxidizes unsaturated ketene dithioacetals in wet MeCN to give cation radicals that cyclize to tri-substituted double bonds and styrenes by cation-like cyclizations leading to cyclic cation radicals that are transformed by further oxidation, hydrolysis and cyclization to bicyclic lactones in moderate to good yield. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00857-7

文献信息

• Enantioselective Synthesis of the Unnatural Enantiomers of the Fungal Sesquiterpenoids Acorenone and Trichoacorenol
  作者：Nelson L. Brock、Jeroen S. Dickschat

  DOI：10.1002/ejoc.201100688

  日期：2011.9

  spirocyclic sesquiterpenoids trichoacorenol, previously identified in Trichoderma koningii (Huang et al., 1995), and acorenone. A new enantioselective synthesis of the enantiomer of the natural spirocyclic sesquiterpene acorenone and the first enantioselective synthesis of the related compound ent-trichoacorenol have been completed by a chiral-pool approach starting from (+)-(R)-pulegone using ring-closing metathesis

  使用闭环汽提装置收集几种木霉属真菌释放的挥发物，并通过 GC-MS 进行分析。大多数研究的菌株都释放了两种结构相关的螺环倍半萜类物质 trichoacorenol，以前在 Trichoderma koningii (Huang et al., 1995) 和 acorenone 中发现。天然螺环倍半萜烯酮对映体的新对映选择性合成和相关化合物ent-trichoacorenol的首次对映选择性合成已通过从(+)-(R)-pulegone开始使用闭环复分解的手性池方法完成作为关键步骤。来自哈茨木霉属的天然滴虫醇的绝对构型。714已通过手性GC-MS分析指定，与T. koningii中的相同。
• Stereospecific synthesis of iridomyrmecin and related iridolactones
  作者：J. Wolinsky、T. Gibson、D. Chan、H. Wolf

  DOI：10.1016/0040-4020(65)80066-7

  日期：1965.1

  Stereospecific syntheses of 6 (I, II, XVI, XXV, XXVI and XXXII) out fo 8 of the possible iridolactones are described. The lactone IV, produced by lactonization of trans-pulegenic acid (III), was converted by LAH reduction and acetylation to 3-(α-hydroxyisopropyl)-2-acetoxymethyl-1-methylcyclopentane (cis-trans-V). Dehydration of V with refluxing acetic anhydride gave 2-acetoxy-methyl-3-isopropenyl

  描述了8种可能的偶氮内酯中的6（I，II，XVI，XXV，XXVI和XXXII）的立体特异性合成。通过反式-产酸（III）的内酯化产生的内酯IV通过LAH还原和乙酰化转化为3-（α-羟基异丙基）-2-乙酰氧基甲基-1-甲基环戊烷（顺式-反式-V）。用回流的乙酸酐将V脱水，得到2-乙酰氧基-甲基-3-异丙烯基-1-甲基环戊烷（顺-反-VII）。VII的氢硼化，然后氧化和水解，得到（-）-iridomyrmecin（I），其与甲醇钠差向异构为（+）-isoiridomyrmecin（II）。该顺式-顺式-iridolactones XXV XXVI和在类似fashiong制作从顺式-顺-内酯XVII。用甲醇中的氯化氢处理内酯IV和XVII，分别得到甲基反式-反式和反式-顺式-氯多菌酸酯X和XXVII。然后将这些酯转化为异氰酸内酯XVI和XXXII。
• ACETALS OF NEPETALIC ACID AND METHOD OF PREPARATION
  申请人：SCIALDONE MARK A.

  公开号：US20090087387A1

  公开（公告）日：2009-04-02

  Disclosed are acetals of nepetalic acid. They may be prepared by reaction of an alcohol with nepetalic acid, and are useful as repellents for insects and arthropods, in addition to other uses.
• US7776912B2
  申请人：——

  公开号：US7776912B2

  公开（公告）日：2010-08-17
• The aphid sex pheromone cyclopentanoids: Synthesis in the elucidation of structure and biosynthetic pathways
  作者：Glenn W. Dawson、John A. Pickett、Diane W.M. Smiley

  DOI：10.1016/0968-0896(96)00012-0

  日期：1996.3

  Identification of a range of aphid sex pheromones as comprising the cyclopentanoids (4aS,7S,7aR)-nepetalactune, (1R,4aS,7S,7aR)-nepetalactol and the (1S)- and (1R,4aR,7S,7aS)-nepetalactols required samples authenticated by H-1 and C-13 NMR. These and related compounds were provided by small scale synthesis and extraction from plants in the genus Nepeta (Lamiaceae). The subsequent discovery that the synthetic sex pheromones could attract males, and also parasitic wasps that attack aphids, has created a need for large scale syntheses of the cyclopentanoids. This is afforded by cyclisation of the 8-oxo-1-enamine of citronellal as originally developed by Schreiber and co-workers (1986). Investigation into the biosynthesis of the cyclopentanoids by plants for exploiting aphid sex pheromones in crop protection by means of molecular biology required synthesis of putative biosynthetic intermediates, some with radioactive isotopic labelling, particularly 8-oxidised monoterpene alcohols and aldehydes. Copyright (C) 1996 Elsevier Science Ltd