(6S,7R)-2,2,6-trimethyl-10-methylenebicyclo[5.4.0]undec-1(11)-ene | 403786-40-3

• 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: (6S,7R)-2,2,6-trimethyl-10-methylenebicyclo[5.4.0]undec-1(11)-ene
• 英文别名: (9S,9aR)-5,5,9-trimethyl-3-methylidene-2,6,7,8,9,9a-hexahydro-1H-benzo[7]annulene
• CAS: 403786-40-3
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: UPQOJPOSKCDZFM-QWHCGFSZSA-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：

  (6S,7R)-2,2,6-trimethyl-10-methylenebicyclo[5.4.0]undec-1(11)-ene 在 四氯苯醌 作用下， 以 苯 为溶剂， 反应 5.0h， 以63%的产率得到(S)-1,1,5,8-tetramethyl-1,2,3,4,5-pentahydrobenzo[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 、 (1R,2S)-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69%的产率得到(6S,7R)-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

• Total Synthesis of Himachalene Sesquiterpenes of<i>Aphthona</i>and<i>Phyllotreta</i>Flea Beetles
  作者：Robert J. Bartelt、David Weisleder、Frank A. Momany

  DOI：10.1055/s-2003-36253

  日期：——

  A total synthesis is presented for himachalene-related norsesquiterpene ketone 1 (racemic), based on the Robinson annulation and other standard reactions. The route involved five steps from cycloheptanone. A favorable result was that the desired diastereomer of 1 was obtained preferentially (97:3) over the unwanted one. Molecular modeling (ab initio calculations) aided in confirming the assignment

  基于 Robinson 环化和其他标准反应，提出了喜马六烯相关的甲基倍半萜酮 1（外消旋）的全合成。该路线涉及环庚酮的五个步骤。一个有利的结果是，所需的非对映异构体 1 优先于 (97:3) 获得，而不是不需要的非对映异构体。分子建模（从头算计算）有助于确认 1 的相对立体化学的分配和合理化观察到的非对映异构体的比例。随后从 1 中产生了三种相关的倍半萜烃和两种醇。这六种化合物天然存在于几种跳蚤甲虫物种中，可能具有信息素功能。
• 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.
• Synthesis and Stereochemistry of the Four Himachalene-Type Sesquiterpenes Isolated from the Flea Beetle (Aphthona flava) as Pheromone Candidates
  作者：Shin-etsu Muto、Masahiko Bando、Kenji Mori

  DOI：10.1002/ejoc.200300812

  日期：2004.5

  8-tetramethyl-1,2,3,4,5,6,5a-heptahydrobenzo[1,2-a][7]annulene (3), and 1,1,5,8-tetramethyl-1,2,3,4,5-pentahydrobenzo[a][7]annulene (ar-himachalene, 4). The stereochemistry of these himachalene-type sesquiterpenes isolated from flea beetles such as Aphthona flava and Phyllotreta cruciferae as their male-pheromone components was revised to (1S,2R)-1, (6R,7S)-2, (5R,5aS)-3, and (R)-4. (© Wiley-VCH Verlag GmbH

  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