(1R,4S,5S)-1,8-二甲基-4-丙-1-烯-2-基-螺[4.5]癸-8-烯 | 24048-44-0

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 中文名称: (1R,4S,5S)-1,8-二甲基-4-丙-1-烯-2-基-螺[4.5]癸-8-烯
• 中文别名: (1R,4S,5S)-1,8-二甲基-4-(丙-1-烯-2-基)螺[4.5]癸-7-烯
• 英文名称: (-)-α-acoradiene
• 英文别名: α-acoradiene；acoradiene；acoradien；Acradien；(1R,4S,5S)-1,8-dimethyl-4-prop-1-en-2-ylspiro[4.5]dec-8-ene
• CAS: 24048-44-0
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: DVBSKQAFCDJNSL-QLFBSQMISA-N

物化性质

• 沸点：
  273.1±20.0 °C(Predicted)
• 密度：
  0.89±0.1 g/cm3(Predicted)
• LogP：
  6.311 (est)
• 保留指数：
  1464;1464;1466;1467;1498;1464

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 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

• 作为反应物：
  描述：

  (1R,4S,5S)-1,8-二甲基-4-丙-1-烯-2-基-螺[4.5]癸-8-烯 在 palladium on activated charcoal 氢气 作用下， 以 正己烷 为溶剂， 反应 1.0h， 生成 1,8-dimethyl-4-propan-2-ylspiro[4.5]decane
  参考文献：
  名称：

  大果柏叶中的倍半萜

  摘要：

  在大果柏的叶子中发现了 10 种倍半萜，其中许多具有不寻常的碳骨架。它们是 (-)-10-epi-β-acoradiene；ent-widdra-2,4(14)-二烯；(E)-异-γ-红没药烯，即(4E)-4-(1,5-二甲基己-5-亚烯基)-1-甲基环己烯；(-)-枯草烯，即(4S)-4-[(1R,2S)-2-异丙烯基-1-甲基环丁基]-1-甲基环己烯；(-)-α-chamipinene，即(1S,6S,7S)-2,2,6,8-四甲基三环[5.3.1.01,6]undec-8-烯；和五个具有 3,3,4'-trimethyl-1,1'-bi(cyclohexyl) 骨架的倍半萜烯，建议将其命名为macrocarpane。讨论了这些倍半萜的可能的单酶生物发生。

  DOI：

  10.1016/j.phytochem.2004.11.002
• 作为产物：
  描述：

  6-氯-2-甲基庚-2-烯 在 叔丁基过氧化氢 、 N-氯代丁二酰亚胺 、 selenium(IV) oxide 、 二甲基硫 、 lithium-sodium alloy 、 2,2,6,6-tetramethylpiperidinyl-lithium 、 氨 、 lithium 作用下， 以 二氯甲烷 为溶剂， 反应 14.87h， 生成 (1R,4S,5S)-1,8-二甲基-4-丙-1-烯-2-基-螺[4.5]癸-8-烯
  参考文献：
  名称：

  （±）-α-Acoradiene的全合成经由分子内光加成和还原环丁烷裂解

  摘要：

  （±）-α-Acoradiene （4）是由3-甲氧基-2-环己烯酮按照8步的顺序合成的。关键步骤（方案6）是区域选择性和立体选择性光[2 + 2]加成物76和还原片段化65。

  DOI：

  10.1002/hlca.19830660213

文献信息

• Sesquiterpene Synthases Cop4 and Cop6 from Coprinus cinereus: Catalytic Promiscuity and Cyclization of Farnesyl Pyrophosphate Geometric Isomers
  作者：Fernando Lopez-Gallego、Sean A. Agger、Daniel Abate-Pella、Mark D. Distefano、Claudia Schmidt-Dannert

  DOI：10.1002/cbic.200900671

  日期：——

  Cyclization of FPP: Two new fungal sesquiterpene synthase are described that have opposite catalytic fidelities in the cyclization of farnesyl diphosphate. Catalytic promiscuity can be drastically reduced by changing the conditions of the reaction. Conversion of the FPP geometric isomers was found to proceed via opposite enantiomers of a cyclic carbocation intermediate that are rearranged to different

  FPP 的环化：描述了两种新的真菌倍半萜烯合酶，它们在二磷酸法呢酯的环化中具有相反的催化保真度。通过改变反应条件可以大大减少催化混杂。发现 FPP 几何异构体的转化是通过环状碳阳离子中间体的相反对映异构体进行的，这些对映异构体重新排列成不同的倍半萜烯产物。
• Bisabolyl-Derived Sesquiterpenes from Tobacco 5-Epi-aristolochene Synthase-Catalyzed Cyclization of (2<i>Z</i>,6<i>E</i>)-Farnesyl Diphosphate
  作者：Juan A. Faraldos、Paul E. O’Maille、Nikki Dellas、Joseph P. Noel、Robert M. Coates

  DOI：10.1021/ja909886q

  日期：2010.3.31

  acyclic allylic alcohols (2Z,6E)-farnesol (6.7%) and nerolidol (3.6%), five cyclic sesquiterpene hydrocarbons and two cyclic sesquiterpene alcohols: (+)-2-epi-prezizaene (44%), (-)-alpha-cedrene (21.5%), (R)-(-)-beta-curcumene (15.5%), alpha-acoradiene (3.9%), 4-epi-alpha-acoradiene (1.3%), and equal amounts of alpha-bisabolol (1.8%) and epi-alpha-bisalolol (1.8%). The structures, stereochemistry, and

  我们报告了由烟草 5-epi-马兜铃烯合酶 (TEAS) 有效催化的前所未有的 1,6-环化（cisoid 途径）产生的七种红没药酰基衍生倍半萜的结构和立体化学。使用 (2Z,6E)-法呢基二磷酸作为重组 TEAS 的替代底物导致强烈的酶促环化作用，生成一系列完全 (>/=99.5%) 来自 cisoid 途径的产物，而这些相同的产物占约. 使用 (2E,6E)-法呢基二磷酸获得的总烃的 2.5%。除了无环烯丙醇 (2Z,6E)-法呢醇 (6.7%) 和橙花醇 (3.6%)、五种环状倍半萜烃和两种环状倍半萜醇外，对 2Z,6E 底物的制备培养提取物进行色谱分离： (+)-2-epi-prezizaene (44%), (-)-α-雪松烯 (21.5%)、(R)-(-)-β-姜黄烯 (15.5%)、α-acoradiene (3.9%)、4-epi-alpha-acoradiene (1.3%)
• RNA-seq discovery, functional characterization, and comparison of sesquiterpene synthases from Solanum lycopersicum and Solanum habrochaites trichomes
  作者：Petra M. Bleeker、Eleni A. Spyropoulou、Paul J. Diergaarde、Hanne Volpin、Michiel T. J. De Both、Philipp Zerbe、Joerg Bohlmann、Vasiliki Falara、Yuki Matsuba、Eran Pichersky、Michel A. Haring、Robert C. Schuurink

  DOI：10.1007/s11103-011-9813-x

  日期：2011.11

  Solanum lycopersicum and Solanum habrochaites (f. typicum) accession PI127826 emit a variety of sesquiterpenes. To identify terpene synthases involved in the production of these volatile sesquiterpenes, we used massive parallel pyrosequencing (RNA-seq) to obtain the transcriptome of the stem trichomes from these plants. This approach resulted initially in the discovery of six sesquiterpene synthase cDNAs from S. lycopersicum and five from S. habrochaites. Searches of other databases and the S. lycopersicum genome resulted in the discovery of two additional sesquiterpene synthases expressed in trichomes. The sesquiterpene synthases from S. lycopersicum and S. habrochaites have high levels of protein identity. Several of them appeared to encode for non-functional proteins. Functional recombinant proteins produced germacrenes, β-caryophyllene/α-humulene, viridiflorene and valencene from (E,E)-farnesyl diphosphate. However, the activities of these enzymes do not completely explain the differences in sesquiterpene production between the two tomato plants. RT-qPCR confirmed high levels of expression of most of the S. lycopersicum sesquiterpene synthases in stem trichomes. In addition, one sesquiterpene synthase was induced by jasmonic acid, while another appeared to be slightly repressed by the treatment. Our data provide a foundation to study the evolution of terpene synthases in cultivated and wild tomato.

  番茄（Solanum lycopersicum）和哈勃罗切特番茄（Solanum habrochaites）（f. typicum）的PI127826品系会释放多种倍半萜。为了鉴定参与这些挥发性倍半萜合成的萜合成酶，我们使用大规模平行测序（RNA-seq）获得了这些植物茎毛的转录组。这种方法最初发现了番茄（S. lycopersicum）的6个倍半萜合成酶cDNA和哈勃罗切特番茄（S. habrochaites）的5个倍半萜合成酶cDNA。通过对其他数据库和番茄（S. lycopersicum）基因组的搜索，又发现了2个在茎毛中表达的倍半萜合成酶。番茄（S. lycopersicum）和哈勃罗切特番茄（S. habrochaites）的倍半萜合成酶具有高度的蛋白质同源性。其中一些似乎编码无功能的蛋白质。功能性重组蛋白从（E,E）-法呢基二磷酸酯中产生香豆素、β-石竹烯/α-胡莫烯、绿花烯和瓦伦烯。然而，这些酶的活性并不能完全解释两种番茄植物在倍半萜合成方面的差异。RT-qPCR证实了番茄（S. ly
• Structural Elucidation of Cisoid and Transoid Cyclization Pathways of a Sesquiterpene Synthase Using 2-Fluorofarnesyl Diphosphates
  作者：Joseph P. Noel、Nikki Dellas、Juan A. Faraldos、Marylin Zhao、B. Andes Hess、Lidia Smentek、Robert M. Coates、Paul E. O’Maille

  DOI：10.1021/cb900295g

  日期：2010.4.16

  Sesquiterpene skeletal complexity in nature originates from the enzyme catalyzed ionization of (trans,trans)-farnesyl diphosphate (FPP) (1a) and subsequent cyclization along either 2,3-transold or 2,3-cisoid farnesyl cation pathways. Tobacco 5-epi-aristolochene synthase (TEAS), a transoid synthase, produces cisoid products as a component of its minor product spectrum. To investigate the cryptic cisoid cyclization pathway in TEAS, we employed (cis,trans)-FPP (1b) as an alternative substrate. Strikingly, TEAS was catalytically robust in the enzymatic conversion of (cis,trans)-FPP (1b) to exclusively (>= 99.5%) cisoid products. Further, crystallographic characterization of wild-type TEAS and a catalytically promiscuous mutant (M4 TEAS) with 2-fluoro analogues of both all-trans FPP (1a) and (cis,trans)-FPP (1b) revealed binding modes consistent with preorganization of the farnesyl chain These results provide a structural glimpse into both cisoid and transoid,cyclization pathways efficiently templated by a single enzyme active site, consistent with the recently elucidated stereochemistry of the cisoid products. Further, computational studies using density functional theory calculations reveal concerted highly asynchronous cyclization pathways leading to the major cisoid cyclization products. The implications of these discoveries for expanded sesquiterpene diversity in nature are discussed.
• Total Synthesis of (±)-α-Acoradiene<i>via</i>Intramolecular Photoaddition and Reductive Cyclobutane Cleavage
  作者：Wolfgang Oppolzer、Freddy Zutterman、Kurt Bättig

  DOI：10.1002/hlca.19830660213

  日期：1983.3.16

  (±)-α-Acoradiene (4) has been synthesized from 3-methoxy-2-cyclohexenone by a sequence of 8 steps. The key steps (Scheme 6) are the regio- and stereoselective photo[2+2]addition 76 and the reductive fragmentation 65.

  （±）-α-Acoradiene （4）是由3-甲氧基-2-环己烯酮按照8步的顺序合成的。关键步骤（方案6）是区域选择性和立体选择性光[2 + 2]加成物76和还原片段化65。