二环[3.1.0]己-2-烯,5-(1,5-二甲基-4-己烯基)-2-甲基- | 159407-35-9

• 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
• 中文名称: 二环[3.1.0]己-2-烯,5-(1,5-二甲基-4-己烯基)-2-甲基-
• 英文名称: 7-epi-sesquithujene
• 英文别名: (1S)-2-methyl-5-[(2R)-6-methylhept-5-en-2-yl]bicyclo[3.1.0]hex-2-ene
• CAS: 159407-35-9
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: UCQHFDKBUHCAFR-ILXRZTDVSA-N

物化性质

• 沸点：
  257.2±7.0 °C(Predicted)
• 密度：
  0.922±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  15
• 可旋转键数：
  4
• 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

• 作为产物：
  描述：

  、 甲基溴化镁 在 iron(III)-acetylacetonate 作用下， 以 四氢呋喃 、 N-甲基吡咯烷酮 、 乙醚 为溶剂， 以4.7 mg的产率得到二环[3.1.0]己-2-烯,5-(1,5-二甲基-4-己烯基)-2-甲基-
  参考文献：
  名称：

  黄金催化的萜类化合物的倍半萜烯和倍半萜烯家族的正式合成，以及雪松烯和雪松酚的合成。

  摘要：

  描述了通过金催化的Ohloff-Rautenstrauch-型烯炔环异构化的方法简单地进入双环环丙基酮衍生物5和6。通过将非支化的烯丙基锌试剂21不对称地添加到由去质子化的双恶唑啉（BOX）配体22介导的炔基醛17中来制备所需的底物。然后将化合物5和6转化为倍半胱氨酸和倍半熟的不同成员的主体。萜类化合物，尤其是在铁催化的交叉偶联反应的帮助下。由于可以清楚地确定5和6的相对和绝对构型，因此合成样品允许解开各种此类萜类化合物以前未知的立体结构，包括顺式倍半萜烯水合物（33），7-表倍半萜烯（36），倍半萜烯B（37）和环氧倍半萜烯（45）。此外，6的制备也构成了塞得烯（11）和塞多尔（12）的正式全合成。

  DOI：

  10.1002/chem.200801382

文献信息

• Isotope sensitive branching and kinetic isotope effects to analyse multiproduct terpenoid synthases from Zea mays
  作者：Nathalie Gatto、Abith Vattekkatte、Tobias Köllner、Jörg Degenhardt、Jonathan Gershenzon、Wilhelm Boland

  DOI：10.1039/c4cc10395e

  日期：——

  Deuterium surrounded carbocations support branching point analyses of multi product terpenoid synthases.

  氘包围的碳正离子支持多产物萜类合酶的分支点分析。
• The Variability of Sesquiterpenes Emitted from Two <i>Zea mays</i> Cultivars Is Controlled by Allelic Variation of Two Terpene Synthase Genes Encoding Stereoselective Multiple Product Enzymes
  作者：Tobias G. Köllner、Christiane Schnee、Jonathan Gershenzon、Jörg Degenhardt

  DOI：10.1105/tpc.019877

  日期：2004.5

  The mature leaves and husks of Zea mays release a complex blend of terpene volatiles after anthesis consisting predominantly of bisabolane-, sesquithujane-, and bergamotane-type sesquiterpenes. The varieties B73 and Delprim release the same volatile constituents but in significantly different proportions. To study the molecular genetic and biochemical mechanisms controlling terpene diversity and distribution in these varieties, we isolated the closely related terpene synthase genes terpene synthase4 (tps4) and tps5 from both varieties. The encoded enzymes, TPS4 and TPS5, each formed the same complex mixture of sesquiterpenes from the precursor farnesyl diphosphate but with different proportions of products. These mixtures correspond to the sesquiterpene blends observed in the varieties B73 and Delprim, respectively. The differences in the stereoselectivity of TPS4 and TPS5 are determined by four amino acid substitutions with the most important being a Gly instead of an Ala residue at position 409 at the catalytic site of the enzyme. Although both varieties contain tps4 and tps5 alleles, their differences in terpene composition result from the fact that B73 has only a single functional allele of tps4 and no functional alleles of tps5, whereas Delprim has only a functional allele of tps5 and no functional alleles of tps4. Lack of functionality was shown to be attributable to frame-shift mutations or amino acid substitutions that greatly reduce the activity of their encoded proteins. Therefore, the diversity of sesquiterpenes in these two maize cultivars is strongly influenced by single nucleotide changes in the alleles of two terpene synthase genes.

  玉米成熟叶片和果壳在开花后释放出一种复杂的萜烯挥发物混合物，主要由红没药烷、倍半萜烷和佛手柑烷类倍半萜组成。B73和Delprim这两个品种释放的挥发物成分相同，但比例明显不同。为了研究控制这些品种中萜烯多样性和分布的分子遗传和生化机制，我们从这两个品种中分离出了密切相关的萜烯合成酶基因terpene synthase4（tps4）和tps5。编码的酶TPS4和TPS5分别从前体法呢基二磷酸形成相同的倍半萜混合物，但产物比例不同。这些混合物分别对应于在B73和Delprim品种中观察到的倍半萜混合物。TPS4和TPS5在立体选择性上的差异是由四个氨基酸取代决定的，其中最重要的是在酶催化位点第409位由甘氨酸取代了丙氨酸残基。虽然这两个品种都含有tps4和tps5等位基因，但它们在萜烯组成上的差异是由于B73只有一个tps4的功能等位基因，而没有tps5的功能等位基因，而Delprim只有一个tps5的功能等位基因，而没有tps4的功能等位基因。功能缺失是由于移码突变或氨基酸取代导致其编码蛋白活性大大降低。因此，这两个玉米栽培品种
• Absolute Configuration of 7-<i>epi</i>-Sesquithujene
  作者：Ashot Khrimian、Allard A. Cossé、Damon J. Crook

  DOI：10.1021/np200098z

  日期：2011.6.24

  7-epi-Sesquithujene (1) is a bicyclic sesquiterpene isolated from phoebe oil, an essential oil of the Brazilian walnut tree, Phoebe porosa. It is also produced by stressed ash trees and has been shown to elicit strong electrophysiological responses on emerald ash borer, Agrilus planipennis, antennae. In the course of the development of a synthetic 7-epi-sesquithujene lure for field testing against the emerald ash borer, we found that the absolute configuration of this compound had not been determined. We isolated >95% pure 7-epi-sesquithujene from phoebe oil via successive fractionation and conventional and argentation (HPLC) chromatographies. The specific optical rotation of this compound matched that of a synthetic product of known configuration. We also synthesized two other stereoisomers of sesquithujene and developed a chiral GC method to separate all four. Based on the specific rotation, stereoselective syntheses, and chiral GC analyses, 7-epi-sesquithujene present in phoebe oil and white ash was found to have the 2S,6S,7R absolute configuration.
• A Gold-Catalyzed Entry into the Sesquisabinene and Sesquithujene Families of Terpenoids and Formal Total Syntheses of Cedrene and Cedrol
  作者：Alois Fürstner、Andreas Schlecker

  DOI：10.1002/chem.200801382

  日期：2008.10.20

  into the bicyclic cyclopropyl ketone derivatives 5 and 6 by way of a gold-catalyzed Ohloff-Rautenstrauch-type enyne cycloisomerization is described. The required substrates were prepared by an asymmetric addition of the branched allylzinc reagent 21 to the alkynyl aldehyde 17 mediated by the deprotonated bisoxazoline (BOX) ligand 22. Compounds 5 and 6 were then converted into a host of different members

  描述了通过金催化的Ohloff-Rautenstrauch-型烯炔环异构化的方法简单地进入双环环丙基酮衍生物5和6。通过将非支化的烯丙基锌试剂21不对称地添加到由去质子化的双恶唑啉（BOX）配体22介导的炔基醛17中来制备所需的底物。然后将化合物5和6转化为倍半胱氨酸和倍半熟的不同成员的主体。萜类化合物，尤其是在铁催化的交叉偶联反应的帮助下。由于可以清楚地确定5和6的相对和绝对构型，因此合成样品允许解开各种此类萜类化合物以前未知的立体结构，包括顺式倍半萜烯水合物（33），7-表倍半萜烯（36），倍半萜烯B（37）和环氧倍半萜烯（45）。此外，6的制备也构成了塞得烯（11）和塞多尔（12）的正式全合成。