(6R,7S)-2,2,6-trimethyl-10-methylenebicyclo[5.4.0]undec-1(11)-ene | 725259-61-0

• 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: (6R,7S)-2,2,6-trimethyl-10-methylenebicyclo[5.4.0]undec-1(11)-ene
• 英文别名: (9R,9aS)-5,5,9-trimethyl-3-methylidene-2,6,7,8,9,9a-hexahydro-1H-benzo[7]annulene
• CAS: 725259-61-0
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: UPQOJPOSKCDZFM-OLZOCXBDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (6R,7S)-2,2,6-trimethyl-10-methylenebicyclo[5.4.0]undec-1(11)-ene 在 甲酸 作用下， 以 甲醇 为溶剂， 以95%的产率得到(5R,5aS)-1,1,5,8-tetramethyl-1,2,3,4,5,5a,6-heptahydrobenzo[1,2-a][7]-annulene
  参考文献：
  名称：

  从跳蚤甲虫 (Aphthona flava) 中分离出的四种喜马偕烯型倍半萜作为信息素候选物的合成和立体化学

  摘要：

  2,6,6-三甲基双环[5.4.0]undec-7-en-9-one (1) 的 (1S,2R) 和 (1R,2S) 异构体均由 (S)- 和 ( R)-香茅醛 (5)，分别。(1R,2S)-(-)-1 的立体化学是通过 X 射线分析确定的；它表现出类似于 cholest-4-en-3-one 的 CD 谱，与其绝对构型一致。酮 (1S,2R)- 和 (1R,2S)-1 被转化为其他三种喜马查烯烃的对映异构体，2,2,6-trimethyl-10-methylenebicyclo[5.4.0]undec-1(11)-烯 (2), 1,1,5,8-四甲基-1,2,3,4,5,6,5a-七氢苯并[1,2-a][7] 环烯 (3), 和 1,1, 5,8-四甲基-1,2,3,4,5-pentahydrobenzo[a][7]annulene (ar-himachalene, 4)。这些喜马偕烯型

  DOI：

  10.1002/ejoc.200300812
• 作为产物：
  描述：

  甲基三苯基溴化膦 、 (1S,2R)-2,2,6-trimethylbicyclo[5.4.0]undec-7-en-9-one 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.5h， 以82%的产率得到(6R,7S)-2,2,6-trimethyl-10-methylenebicyclo[5.4.0]undec-1(11)-ene
  参考文献：
  名称：

  从跳蚤甲虫 (Aphthona flava) 中分离出的四种喜马偕烯型倍半萜作为信息素候选物的合成和立体化学

  摘要：

  2,6,6-三甲基双环[5.4.0]undec-7-en-9-one (1) 的 (1S,2R) 和 (1R,2S) 异构体均由 (S)- 和 ( R)-香茅醛 (5)，分别。(1R,2S)-(-)-1 的立体化学是通过 X 射线分析确定的；它表现出类似于 cholest-4-en-3-one 的 CD 谱，与其绝对构型一致。酮 (1S,2R)- 和 (1R,2S)-1 被转化为其他三种喜马查烯烃的对映异构体，2,2,6-trimethyl-10-methylenebicyclo[5.4.0]undec-1(11)-烯 (2), 1,1,5,8-四甲基-1,2,3,4,5,6,5a-七氢苯并[1,2-a][7] 环烯 (3), 和 1,1, 5,8-四甲基-1,2,3,4,5-pentahydrobenzo[a][7]annulene (ar-himachalene, 4)。这些喜马偕烯型

  DOI：

  10.1002/ejoc.200300812

文献信息

• Novel family of terpene synthases evolved from <i>trans</i> -isoprenyl diphosphate synthases in a flea beetle
  作者：Franziska Beran、Peter Rahfeld、Katrin Luck、Raimund Nagel、Heiko Vogel、Natalie Wielsch、Sandra Irmisch、Srinivasan Ramasamy、Jonathan Gershenzon、David G. Heckel、Tobias G. Köllner

  DOI：10.1073/pnas.1523468113

  日期：2016.3.15

  Whether insect sesquiterpenes are synthesized de novo, derived from plant precursors, or produced by symbionts is often unknown. We identified an evolutionarily novel terpene synthase gene family in the striped flea beetle, a notorious pest of Brassica crops in North America and Asia, and one of these genes was shown to be directly involved in the biosynthesis of the male-specific sesquiterpene aggregation pheromone. Phylogenetic and gene structure analyses indicate that an expansion of the trans -isoprenyl diphosphate synthase gene family in the ancestor of the subfamily Galerucinae enabled functional diversification toward this terpene synthase gene family. These insights into how flea beetles synthesize their aggregation pheromones may lead to new approaches for pest management.

  无论昆虫倍半萜是通过新合成、从植物前体中衍生或由共生菌产生，通常都是未知的。我们在斑纹跳蚤甲中鉴定出了一种进化上新颖的萜类合成酶基因家族，这是北美和亚洲油菜作物的臭名昭著害虫之一，其中一个基因被证明直接参与了雄性特异性倍半萜聚集信息素的生物合成。系统发育和基因结构分析表明，在长臂叶甲亚科祖先中，转 -异戊烯基二磷酸合酶基因家族的扩张使得功能多样化朝着这个萜类合成酶基因家族发展。对斑纹跳蚤如何合成其聚集信息素的这些见解可能会导致新的害虫管理方法。

• Male-Specific Sesquiterpenes from <i>Phyllotreta</i> Flea Beetles
  作者：Robert J. Bartelt、Bruce W. Zilkowski、Allard A. Cossé、Udo Schnupf、Karl Vermillion、Frank A. Momany

  DOI：10.1021/np100608p

  日期：2011.4.25

  Flea beetles in several genera are known to possess male-specific sesquiterpenes, at least some of Which serve as aggregation, pheromones that attract both sexes. In continuing, research on the Chemical ecology of Phyllotreta flea beetles, six new male specific sesquiterpenes were identified, one from P. striolata (hydroxyketone 9) and five from P. pusilla (aldehydes 10-12 and 14 and alcohol 13),, both species are crop pests. The minute amounts from beetles provided mass. spectra, and chromatographic data but were insufficient for complete structure determination. However, it was discovered that the new compounds could all be produced by applying organic reactions to previously identified flea, beetle sesquiterpenes, and the resulting, larger amounts of material permitted, definitive. structure analysis by NMR. Molecular Modeling was used in conjunction with NMR to define relative configurations of several newly created stereogenic centers. The absolute configurations of natural 9-14 were established by chiral gas chromatography/. mass spectrometry. In electrophysiologicial tests (GC-EAD) conducted with P. striolata compound 9, was detected with high, sensitivity by) the beetle;antennae, which is consistent with a pheromonal function.,The research opens new possibilities. for using behavioral Chemicals to monitor or Manage these pest species.