(2S,4aR,8aR)-4a,8-dimethyl-2-(prop-1-en-2-yl)-1,2,3,4,4a,5,6,8a-octahydronaphthalene | 123123-37-5

• 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: (2S,4aR,8aR)-4a,8-dimethyl-2-(prop-1-en-2-yl)-1,2,3,4,4a,5,6,8a-octahydronaphthalene
• 英文别名: (2S,4aR,8aR)4a,8-dimethyl-2-(prop-1-en-2-yl)-1,2,3,4,4a,5,6,8a-octahydronaphthalene；7–epi–a–selinene；(-)-7-epi-α-selinene；(-)7-epi-α-selinene；7-epi-α-selinene；7-epi-alpha-selinene；(-)-7-Epi-alpha-selinene；(3S,4aR,8aR)-5,8a-dimethyl-3-prop-1-en-2-yl-2,3,4,4a,7,8-hexahydro-1H-naphthalene
• CAS: 123123-37-5
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: OZQAPQSEYFAMCY-SOUVJXGZSA-N

物化性质

• 沸点：
  270.0±0.0 °C(Predicted)
• 密度：
  0.888±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  15
• 可旋转键数：
  1
• 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：

  ent-5-hydroxy-10α-eudesm-11-en-3-one 在 盐酸 、 sodium tetrahydroborate 、 乙醇 、 氨 、 lithium 、 lithium carbonate 、 lithium bromide 作用下， 以 吡啶 、 甲醇 、 乙醚 、 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 13.83h， 生成 (2S,4aR,8aR)-4a,8-dimethyl-2-(prop-1-en-2-yl)-1,2,3,4,4a,5,6,8a-octahydronaphthalene
  参考文献：
  名称：

  Enantioselective Total Syntheses of (−)-7βH-Eudesmane-4α,11-diol and (+)-ent-7βH-Eudesmane-4α,11-diol

  摘要：

  The syntheses of (-)-7 beta H-eudesmane-4 alpha,11-diol (2) and (+)-ent-7 beta H-eudesmane-4 alpha,11-diol (ent-2) were carried out starting from (-)- and (+)-dihydrocarvones. As a result, the structure, including absolute configuration, of the naturally occurring eudesmane-4,11-diol isolated from Pluchea arguta was determined to be (+)-ent-7 beta H-eudesmane-4 alpha,11-diol (ent-2).

  DOI：

  10.1021/np9702906

文献信息

• The bouquet of grapevine ( <i>Vitis vinifera</i> L. cv. Cabernet Sauvignon) flowers arises from the biosynthesis of sesquiterpene volatiles in pollen grains
  作者：Diane M. Martin、Omid Toub、Angela Chiang、Bernard C. Lo、Sebastian Ohse、Steven T. Lund、Jörg Bohlmann

  DOI：10.1073/pnas.0901387106

  日期：2009.4.28

  Terpenoid volatiles are important information molecules that enable pollinators to locate flowers and may protect reproductive tissues against pathogens or herbivores. Inflorescences of grapevine ( Vitis vinifera L.) are composed of tiny green flowers that produce an abundance of sesquiterpenoid volatiles. We demonstrate that male flower parts of grapevines are responsible for sesquiterpenoid floral scent formation. We describe temporal and spatial patterns of biosynthesis and release of floral volatiles throughout the blooming of V. vinifera L. cv. Cabernet Sauvignon. The biosynthesis of sesquiterpene volatiles, which are emitted with a light-dependent diurnal pattern early in the morning at prebloom and bloom, is localized to anthers and, more specifically, within the developing pollen grains. Valencene synthase (VvValCS) enzyme activity, which produces the major sesquiterpene volatiles of grapevine flowers, is present in anthers. VvValCS transcripts are most abundant in flowers at prebloom stages. Western blot analysis identified VvValCS protein in anthers, and in situ immunolabeling located VvValCS protein in pollen grains during bloom. Histochemical staining, as well as immunolabeling analysis by fluorescent microscopy and transmission electron microscopy, indicated that VvValCS localizes close to lipid bodies within the maturing microspore.

  萜烯挥发性物质是重要的信息分子，使传粉者能够找到花朵，并可能保护生殖组织免受病原体或食草动物的侵害。葡萄藤（Vitis vinifera L.）的花序由微小的绿色花朵组成，产生大量的倍半萜烯挥发性物质。我们证明了葡萄藤的雄性花部负责倍半萜烯花香的形成。我们描述了在Cabernet Sauvignon葡萄品种的盛开期间，花香挥发物的生物合成和释放的时间和空间模式。倍半萜烯挥发性物质的生物合成，其在盛开前和盛开期早晨以光依赖性昼夜节律发出，局限于花药和更具体地说是在发育的花粉颗粒内部。瓦伦西烯合酶（VvValCS）酶活性，产生葡萄藤花朵的主要倍半萜烯挥发性物质，在花药中存在。VvValCS转录本在盛开前的花朵中最丰富。Western blot分析确定了花药中VvValCS蛋白质，原位免疫标记定位了VvValCS蛋白质在盛开期间的花粉颗粒中。组织化学染色以及荧光显微镜和透射电镜的免疫标记分析表明，VvValCS定位在成熟的小孢子附近的脂肪体上。
• Germacrene A Is a Product of the Aristolochene Synthase-Mediated Conversion of Farnesylpyrophosphate to Aristolochene
  作者：Melanie J. Calvert、Peter R. Ashton、Rudolf K. Allemann

  DOI：10.1021/ja020762p

  日期：2002.10.1

  The biosynthesis of several sesquiterpenes has been proposed to proceed via germacrene A. However, to date, the production of germacrene A has not been proven directly for any of the sesquiterpene synthases for which it was postulated as an intermediate. We demonstrate here for the first time that significant amounts of germacrene A (7.5% of the total amount of products) are indeed released from wild-type aristolochene synthase (AS) from Penicillium roqueforti. Germacrene A was identified through direct GC-MS comparison to an authentic sample and through production of beta-elemene in a thermal Cope rearrangement. AS also produced a small amount of valencene through deprotonation of C6 rather than C8 in the final step of the reaction. On the basis of the X-ray structure of AS, Tyr 92 was postulated to be the active-site acid responsible for protonation of germacrene A (Caruthers, J. M.; Kang, L; Rynkiewicz, M. J.; Cane, D. E.; Christianson, D. W. J. Biol. Chem. 2000, 275, 25533-25539). The CID spectra of a mutant protein, ASY92F, in which Tyr 92 was replaced by Phe, and of AS were very similar. ASY92F was approximately 0.1% as active as nonmutated recombinant AS. The steady-state kinetic parameters were measured as 0.138 min(-1) and 0.189 mM for k(cat) and K-M, respectively. Similar to a mutant protein of 5-epiaristolochene (Rising, K. A.; Starks, C. M.; Noel, J. P.; Chappell, J. J. Am. Chem. Soc. 2000, 122, 1861 1866), the mutant released significant amounts of germacrene A (similar to29%). ASY92F also produced various amounts of a further five hydrocarbons of molecular weight 204, valencene, beta-(E)-farnesene, alpha- and beta-selinene, and selina-4,11-diene.
• Vitis vinifera terpenoid cyclases: functional identification of two sesquiterpene synthase cDNAs encoding (+)-valencene synthase and (−)-germacrene D synthase and expression of mono- and sesquiterpene synthases in grapevine flowers and berries
  作者：Joost Lücker、Pat Bowen、Jörg Bohlmann

  DOI：10.1016/j.phytochem.2004.08.017

  日期：2004.10

  Valencene is a volatile sesquiterpene emitted from flowers of grapevine, Vitis vinifera L. A full-length cDNA from the cultivar Gewurztraminer was functionally expressed in Escherichia coli and found to encode valencene synthase (VvVal). The two major products formed by recombinant VvVal enzyme activity with farnesyl diphosphate (FPP) as substrate are (+)-valencene and (-)7-epi-alpha-selinene. Grapevine valencene synthase is closely related to a second sesquiterpene synthase from this species, (-)-germacrene D synthase (VvGerD). VvVal and VvGerD cDNA probes revealed strong signals in Northern hybridizations with RNA isolated from grapevine flower buds. Transcript levels were lower in open pre-anthesis flowers, flowers after anthesis, or at early onset of fruit development. Similar results were obtained using a third probe, (-)-alpha-terpineol synthase, a monoterpenol synthase. Sesquiterpene synthase and monoterpene synthase transcripts were not detected in the mesocarp and exocarp during early stages of fruit development, but transcripts hybridizing with VvVal appeared during late ripening of the berries. Sesquiterpene synthase transcripts were also detected in young seeds. (C) 2004 Elsevier Ltd. All rights reserved.
• Enantioselective Total Syntheses of (−)-7β<i>H</i>-Eudesmane-4α,11-diol and (+)-<i>ent</i>-7β<i>H</i>-Eudesmane-4α,11-diol
  作者：Fumito Shimoma、Hisao Kondo、Saori Yuuya、Toshio Suzuki、Hisahiro Hagiwara、Masayoshi Ando

  DOI：10.1021/np9702906

  日期：1998.1.1

  The syntheses of (-)-7 beta H-eudesmane-4 alpha,11-diol (2) and (+)-ent-7 beta H-eudesmane-4 alpha,11-diol (ent-2) were carried out starting from (-)- and (+)-dihydrocarvones. As a result, the structure, including absolute configuration, of the naturally occurring eudesmane-4,11-diol isolated from Pluchea arguta was determined to be (+)-ent-7 beta H-eudesmane-4 alpha,11-diol (ent-2).