Β- 倍半水芹烯 | 20307-83-9

• 物质功能分类: 化学试剂 - 有机试剂 - 烯烃（环状与无环状）
• 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: Β- 倍半水芹烯
• 中文别名: Β-倍半水芹烯
• 英文名称: β-sesquiphellandrene
• 英文别名: beta-sesquiphellandrene；sesquiphellandrene；β-sesquiphallandrene；(-)-beta-Sesquiphellandrene；(3R)-3-[(2S)-6-methylhept-5-en-2-yl]-6-methylidenecyclohexene
• CAS: 20307-83-9
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: PHWISBHSBNDZDX-LSDHHAIUSA-N

物化性质

• 沸点：
  90-90.5 °C(Press: 1 Torr)
• 密度：
  0.8760 g/cm3(Temp: 25 °C)
• 溶解度：
  可溶于氯仿、乙酸乙酯（少许）、甲醇（少许）
• LogP：
  6.522 (est)
• 保留指数：
  1537

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  (3S,6R,7S)-1,10-bisaboladien-3-ol 在 吡啶 、 三氯氧磷 作用下， 以36%的产率得到Β- 倍半水芹烯
  参考文献：
  名称：

  Discovery of the Aggregation Pheromone of the Brown Marmorated Stink Bug (Halyomorpha halys) through the Creation of Stereoisomeric Libraries of 1-Bisabolen-3-ols

  摘要：

  We describe a novel and straightforward route to all stereoisomers of 1,10-bisaboladien-3-ol and 10,11-epoxy-1-bisabolen-3-ol via the rhodium-catalyzed asymmetric addition of trimethylaluminum to diastereomeric mixtures of cyclohex-2-enones 1 and 2. The detailed stereoisomeric structures of many natural sesquiterpenes with the bisabolane skeleton were previously unknown because of the absence of stereoselective syntheses of individual stereoisomers. Several of the bisabolenols are pheromones of economically important pentatomid bug species. Single-crystal X-ray crystallography of underivatized triol 13 provided unequivocal proof of the relative and absolute configurations. Two of the epoxides, (3S,6S,7R,10S)-10,11-epoxy-1-bisabolen-3-ol (3) and (3R,6S,7R,10S)-10,11-epoxy-1-bisabolen-3-ol (4), were identified as the main components of a male-produced aggregation pheromone of the brown marmorated stink bug, Halyomorpha halys, using GC analyses on enantioselective columns. Both compounds attracted female, male, and nymphal H. halys in field trials. Moreover, mixtures of stereoisomers containing epoxides 3 and 4 were also attractive to H. halys, signifying that the presence of additional stereoisomers did not hinder attraction of H. halys and relatively inexpensive mixtures can be used in monitoring, as well as control strategies. H. halys is a polyphagous invasive species in the U.S. and Europe that causes severe injury to fruit, vegetables, and field crops and is also a serious nuisance pest.

  DOI：

  10.1021/np5003753

文献信息

• Structure of Epi-Isozizaene Synthase from <i>Streptomyces coelicolor</i> A3(2), a Platform for New Terpenoid Cyclization Templates^,
  作者：Julie A. Aaron、Xin Lin、David E. Cane、David W. Christianson

  DOI：10.1021/bi902088z

  日期：2010.3.2

  binding and catalysis in a bacterial terpenoid cyclase. Moreover, the binding interactions of BTAC may mimic those of a carbocation intermediate in catalysis. Accordingly, the aromatic rings of F95, F96, and F198 appear to be well-oriented to stabilize carbocation intermediates in the cyclization cascade through cation−π interactions. Mutagenesis of aromatic residues in the enzyme active site results in the

  重组表异齐扎烯合酶 (EIZS) 是一种来自天蓝色链霉菌A3(2) 的倍半萜环化酶，其 X 射线晶体结构已在 1.60 Å 分辨率下确定。具体而言，野生型 EIZS 的结构是其与三个 Mg 2+离子、无机焦磷酸盐 (PP i), 和苄基三乙基铵阳离子 (BTAC)。此外，D99N EIZS 的结构已在 1.90 Å 分辨率下以开放的无配体构象确定。这两种结构的比较提供了细菌萜类环化酶中底物结合和催化所需的构象变化的第一个视图。此外，BTAC 的结合相互作用可能模仿催化中碳阳离子中间体的结合相互作用。因此，F95、F96 和 F198 的芳环似乎很好地定向以通过阳离子-π 相互作用稳定环化级联中的碳阳离子中间体。由于碳阳离子中间体的稳定模式改变以及法尼基二磷酸环化的模板改变，酶活性位点中芳香族残基的诱变导致替代倍半萜产物阵列的产生。因此，F198A EIZS 在具有三个 Mg 的复合物中的 1
• Dynamic evolution of herbivore‐induced sesquiterpene biosynthesis in sorghum and related grass crops
  作者：Xiaofeng Zhuang、Tobias G. Köllner、Nan Zhao、Guanglin Li、Yifan Jiang、Liucun Zhu、Jianxin Ma、Jörg Degenhardt、Feng Chen

  DOI：10.1111/j.1365-313x.2011.04771.x

  日期：2012.1

  Sorghum (Sorghum bicolor) plants damaged by insects emit a blend of volatiles, predominantly sesquiterpenes, that are implicated in attracting natural enemies of the attacking insects. To characterize sesquiterpene biosynthesis in sorghum, seven terpene synthase (TPS) genes, SbTPS1 through SbTPS7, were identified based on their evolutionary relatedness to known sesquiterpene synthase genes from maize and rice. While SbTPS6 and SbTPS7 encode truncated proteins, all other TPS genes were determined to encode functional sesquiterpene synthases. Both SbTPS1 and SbTPS2 produced the major products zingiberene, β‐bisabolene and β‐sesquiphellandrene, but with opposite ratios of zingiberene to β‐sesquiphellandrene. SbTPS3 produced (E)‐α‐bergamotene and (E)‐β‐farnesene. SbTPS4 formed (E)‐β‐caryophyllene as the major product. SbTPS5 produced mostly (E)‐α‐bergamotene and (Z)‐γ‐bisabolene. Based on the genome sequences of sorghum, maize and rice and the sesquiterpene synthase genes they contain, collinearity analysis identified the orthologs of sorghum sesquiterpene synthase genes, except for SbTPS4, in maize and rice. Phylogenetic analysis implied that SbTPS1, SbTPS2 and SbTPS3, which exist as tandem repeats, evolved as a consequence of local gene duplication in a lineage‐specific manner. Structural modeling and site‐directed mutagenesis experiments revealed that three amino acids in the active site play critical roles in defining product specificity of SbTPS1, SbTPS2, SbTPS3 and their orthologs in maize and rice. The naturally occurring functional variations of sesquiterpene synthases within and between species suggest that multiple mechanisms, including lineage‐specific gene duplication, subfunctionalization, neofunctionalization and pseudogenization of duplicated genes, have all played a role in the dynamic evolution of insect‐induced sesquiterpene biosynthesis in grasses.

  摘要受昆虫危害的高粱（Sorghum bicolor）植株会释放出一种混合挥发物，主要是倍半萜，这种挥发物具有吸引天敌昆虫的作用。为了描述高粱倍半萜生物合成的特征，研究人员根据与玉米和水稻中已知倍半萜合成酶基因的进化亲缘关系，确定了七个萜烯合成酶（TPS）基因，即 SbTPS1 至 SbTPS7。虽然 SbTPS6 和 SbTPS7 编码截短蛋白，但所有其他 TPS 基因都被确定编码功能性倍半萜合成酶。SbTPS1 和 SbTPS2 产生的主要产物为紫丁香烯、β-bisabolene 和 β-sesquiphellandrene，但紫丁香烯和β-sesquiphellandrene 的比例相反。SbTPS3 产生 (E)-α-bergamotene 和 (E)-β-法呢烯。SbTPS4 的主要产物是(E)-β-石竹烯。SbTPS5 主要产生 (E)-α-bergamotene 和 (Z)-γ-bisabolene。根据高粱、玉米和水稻的基因组序列及其所含的倍半萜合成酶基因，通过比对分析确定了除 SbTPS4 外，高粱倍半萜合成酶基因在玉米和水稻中的直向同源物。系统进化分析表明，SbTPS1、SbTPS2 和 SbTPS3 以串联重复的形式存在，它们是以特定世系的方式由局部基因重复进化而来的。结构建模和定点突变实验表明，活性位点上的三个氨基酸在确定 SbTPS1、SbTPS2、SbTPS3 及其在玉米和水稻中的同源物的产物特异性方面起着关键作用。倍半萜合成酶在物种内和物种间自然发生的功能变异表明，在昆虫诱导的禾本科植物倍半萜生物合成的动态进化过程中，包括特定品系的基因复制、亚功能化、新功能化和复制基因的假基因化在内的多种机制都发挥了作用。
• Discovery of the Aggregation Pheromone of the Brown Marmorated Stink Bug (<i>Halyomorpha halys</i>) through the Creation of Stereoisomeric Libraries of 1-Bisabolen-3-ols
  作者：Ashot Khrimian、Aijun Zhang、Donald C. Weber、Hsiao-Yung Ho、Jeffrey R. Aldrich、Karl E. Vermillion、Maxime A. Siegler、Shyam Shirali、Filadelfo Guzman、Tracy C. Leskey

  DOI：10.1021/np5003753

  日期：2014.7.25

  We describe a novel and straightforward route to all stereoisomers of 1,10-bisaboladien-3-ol and 10,11-epoxy-1-bisabolen-3-ol via the rhodium-catalyzed asymmetric addition of trimethylaluminum to diastereomeric mixtures of cyclohex-2-enones 1 and 2. The detailed stereoisomeric structures of many natural sesquiterpenes with the bisabolane skeleton were previously unknown because of the absence of stereoselective syntheses of individual stereoisomers. Several of the bisabolenols are pheromones of economically important pentatomid bug species. Single-crystal X-ray crystallography of underivatized triol 13 provided unequivocal proof of the relative and absolute configurations. Two of the epoxides, (3S,6S,7R,10S)-10,11-epoxy-1-bisabolen-3-ol (3) and (3R,6S,7R,10S)-10,11-epoxy-1-bisabolen-3-ol (4), were identified as the main components of a male-produced aggregation pheromone of the brown marmorated stink bug, Halyomorpha halys, using GC analyses on enantioselective columns. Both compounds attracted female, male, and nymphal H. halys in field trials. Moreover, mixtures of stereoisomers containing epoxides 3 and 4 were also attractive to H. halys, signifying that the presence of additional stereoisomers did not hinder attraction of H. halys and relatively inexpensive mixtures can be used in monitoring, as well as control strategies. H. halys is a polyphagous invasive species in the U.S. and Europe that causes severe injury to fruit, vegetables, and field crops and is also a serious nuisance pest.