(11R)-11,13-dihydroxy-guaiane-4(15),10(14)-dien-6,12-olide | 96552-47-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (11R)-11,13-dihydroxy-guaiane-4(15),10(14)-dien-6,12-olide
• 英文别名: (3R,3aR,6aR,9aR,9bR)-3-hydroxy-3-(hydroxymethyl)-6,9-dimethylidene-3a,4,5,6a,7,8,9a,9b-octahydroazuleno[4,5-b]furan-2-one
• CAS: 96552-47-5
• 化学式: C₁₅H₂₀O₄
• 分子量: 264.321
• InChiKey: RQNNFZZLPUJGMA-KBRXKUPHSA-N

物化性质

• 沸点：
  418.4±45.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-bromo-4-methyl-2H-furan-5-one 、 (11R)-11,13-dihydroxy-guaiane-4(15),10(14)-dien-6,12-olide 在 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 以7.5%的产率得到
  参考文献：
  名称：

  New Chemical Clues for Broomrape-Sunflower Host−Parasite Interactions: Synthesis of Guaianestrigolactones

  摘要：

  A comparative structure-activity relationship (SAR) study has been conducted with several guaianolide sesquiterpene lactones (SLs) as inducers of the germination of sunflower broomrape (Orobanche cumana) seeds. Compounds were selected and synthesized to study the influence of the lactone-enol-gamma-lactone moiety on the selectivity of SLs toward the stimulation of sunflower broomrape germination. The results clearly illustrate that SLs are recognized only by O. cumana, while the introduction of a strigol-like second lactone moiety in the guaianolide backbone results in the loss of specificity and hence the germination of other broomrape species. We have named this new class of compounds guaianestrigolactones (GELs).

  DOI：

  10.1021/jf900870j
• 作为产物：
  描述：

  dehydrocostuslactone 在 sodium carbonate 作用下， 以 六甲基磷酰三胺 为溶剂， 反应 168.0h， 以21%的产率得到(11S)-13-hydroxy-guaiane-4(15),10(14)-dien-6,12-olide
  参考文献：
  名称：

  通过亲核羟基的迈克尔加成，可轻松获得具有生物活性的13-羟基和11,13-二羟基倍半萜烯内酯（SLs）

  摘要：

  通过在α-亚甲基-γ-内酯系统中加成迈克尔基，向α，β-不饱和羰基系统中添加羟基可轻松获得新的生物活性双官能倍半萜烯内酯（SLs）。讨论了使用HMPA增强羟基的亲核性质并稳定烯醇化物。另外，我们根据获得的实验数据提出了该机制的建议。该反应的范围和有用性与其他底物一起探索，并受到对一定水平位阻以避免链缩聚的需求的限制。然而，该反应可与酯，酮和醛一起使用。通过X射线衍射分析已经阐明了某些产物的绝对立体化学。

  DOI：

  10.1016/j.tet.2008.09.024

文献信息

• Sesquiterpene Lactones with Potential Use as Natural Herbicide Models. 2. Guaianolides
  作者：Francisco A. Macías、Juan C. G. Galindo、Diego Castellano、Raúl F. Velasco

  DOI：10.1021/jf0005364

  日期：2000.11.1

  A structure-activity study to evaluate the effect of 17 guaianolide sesquiterpene lactones (in a range of 100-0.001 muM) on the growth and germination of several mono- and dicotyledon target species is accomplished. Results are compared with those obtained in the same bioassay with an internal standard, the commercial herbicide Logran, to validate the results with a known active formulation and to compare the results with a commercial product to test their potential use as natural herbicide models. Specific conditions for the selective mono- or polyhydroxylation of guaianolides using the SeO2/tert-butyl hydroperoxide system are presented and discussed. The high regio- and stereoselectivities of the reaction are explained through the specific structural requirements of the bulky first adduct formed during the ene reaction. These compounds appear to have deeper effects on the growth of either monocots or dicots than the previously tested germacranolides. Otherwise, the lactone group seems to be necessary for the activity, though it does not necessarily need to be unsaturated. However, the presence of a second and easily accessible unsaturated carbonyl system greatly enhances the inhibitory activity. Lipophilicity and the stereochemistry of the possible anchoring sites are also crucial factors for the activity. Finally, the levels of growth inhibition obtained with some compounds on dicots or monocots are totally comparable to those of Logran and allow proposing them as lead compounds.
• An easy access to bioactive 13-hydroxylated and 11,13-dihydroxylated sesquiterpene lactones (SLs) through Michael addition of a nucleophilic hydroxyl group
  作者：Francisco A. Macías、María D. García-Díaz、Guillermo M. Massanet、José F. Gómez-Madero、Frank R. Fronczek、Juan C.G. Galindo

  DOI：10.1016/j.tet.2008.09.024

  日期：2008.12

  The addition of a hydroxyl group to α,β-unsaturated carbonyl systems provides a new and easy access to bioactive difunctionalized sesquiterpene lactones (SLs) through a Michael addition to the α-methylene-γ-lactone system. The use of HMPA to enhance the nucleophilic properties of the hydroxyl groups and to stabilize the enolate is discussed. Also, we present a proposal for the mechanism based on the

  通过在α-亚甲基-γ-内酯系统中加成迈克尔基，向α，β-不饱和羰基系统中添加羟基可轻松获得新的生物活性双官能倍半萜烯内酯（SLs）。讨论了使用HMPA增强羟基的亲核性质并稳定烯醇化物。另外，我们根据获得的实验数据提出了该机制的建议。该反应的范围和有用性与其他底物一起探索，并受到对一定水平位阻以避免链缩聚的需求的限制。然而，该反应可与酯，酮和醛一起使用。通过X射线衍射分析已经阐明了某些产物的绝对立体化学。
• New Chemical Clues for Broomrape-Sunflower Host−Parasite Interactions: Synthesis of Guaianestrigolactones
  作者：Francisco A. Macías、María D. García-Díaz、Alejandro Pérez-de-Luque、Diego Rubiales、Juan C. G. Galindo

  DOI：10.1021/jf900870j

  日期：2009.7.8

  A comparative structure-activity relationship (SAR) study has been conducted with several guaianolide sesquiterpene lactones (SLs) as inducers of the germination of sunflower broomrape (Orobanche cumana) seeds. Compounds were selected and synthesized to study the influence of the lactone-enol-gamma-lactone moiety on the selectivity of SLs toward the stimulation of sunflower broomrape germination. The results clearly illustrate that SLs are recognized only by O. cumana, while the introduction of a strigol-like second lactone moiety in the guaianolide backbone results in the loss of specificity and hence the germination of other broomrape species. We have named this new class of compounds guaianestrigolactones (GELs).