毕澄茄烯 | 13744-15-5

• 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
• 中文名称: 毕澄茄烯
• 英文名称: β-cubebene
• 英文别名: beta-cubebene；β-cubenene；β‐cubebene；(1R,5S,6R,7S,10R)-10-methyl-4-methylidene-7-propan-2-yltricyclo[4.4.0.01,5]decane
• CAS: 13744-15-5
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: FSRZGYRCMPZNJF-KHMAMNHCSA-N

物化性质

• 沸点：
  266.9±7.0 °C(Predicted)
• 密度：
  0.93±0.1 g/cm3(Predicted)
• LogP：
  6.181 (est)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.87
• 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：

  大麻 、 毕澄茄烯 、 α-芹子烯 、 selina-3,7(11)-diene 、 (1S,8aR)-1-异丙基-4,7-二甲基-1,2,3,5,6,8a-六氢萘 、 α-愈创木烯 生成 germacrene C
  参考文献：
  名称：

  Sesquiterpene synthases from grand fir (abies grandis), and methods of use

  摘要：

  从大冷杉（Abies grandis）中分离和测序了编码E-α-双萜烯合酶、δ-塞林烯合酶和γ-蒿莲烯合酶的cDNA，并确定了相应的氨基酸序列。因此，提供了编码大冷杉（Abies grandis）中的E-α-双萜烯合酶（SEQ ID No：13）、δ-塞林烯合酶（SEQ ID No：20）和γ-蒿莲烯合酶（SEQ ID No：24）表达的分离DNA序列（SEQ ID No：12；SEQ ID No：19和SEQ ID No：23）。在其他方面，提供了可复制的重组克隆载体，其编码E-α-双萜烯合酶、δ-塞林烯合酶和γ-蒿莲烯合酶，或编码与E-α-双萜烯合酶、δ-塞林烯合酶或γ-蒿莲烯合酶DNA或RNA的至少一部分足够互补的碱基序列，以使其与之杂交。在其他方面，提供了经改造的宿主细胞，它们已经转化、转染、感染和/或注入了重组克隆载体和/或编码E-α-双萜烯合酶、δ-塞林烯合酶或γ-蒿莲烯合酶的DNA序列。因此，提供了用于重组表达前述重组倍半萜合酶的系统和方法，可用于促进它们的大量生产、分离和纯化。重组E-α-双萜烯合酶、δ-塞林烯合酶和γ-蒿莲烯合酶可用于在植物中获得E-α-双萜烯合酶、δ-塞林烯合酶和γ-蒿莲烯合酶的表达或增强表达，以增强倍半萜类物质的生产，或者可用于调节或表达E-α-双萜烯合酶、δ-塞林烯合酶和γ-蒿莲烯合酶，或其产物的生产。

  公开号：

  US20020038001A1
• 作为产物：
  描述：

  Caran-2-spiro-2'-tetrahydrofuran-5'-on 在 Wilkinson's catalyst 氢气 作用下， 生成 毕澄茄烯
  参考文献：
  名称：

  立方烷型倍半萜类化合物的合成及立方醇的立体化学

  摘要：

  已完成从（-）-反-caran-2-one（IX）完全合成立方烷型倍半萜类化合物，即α-和β-立方苯甲酸酯（II）和（III），以及cubebol（I）。Carane-2-spiro-2'-tetrahydrofuran-5'-one（XII）（具有反式-烷结构）的热裂解导致甲基3-（反式-p-mentha-2,8-dien-2-yl丙酸酯（XV），将其转化为相应的重氮酮（XVI）。铜催化的重氮酮的分解导致形成分子内加成产物的混合物，其中一种在氢化后得到反式-7-异丙基-10-甲基三环[4,4,0,0 1,5] decan-4-one（norcubebanone）（XVIIIa），此合成的关键中间体。立方苯甲酸酯和立方波贝是由降冰片烷酮合成的，并且立体选择性的合成过程为这些倍半萜的立体化学提供了合成证据。

  DOI：

  10.1039/p19720001721

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。
• Epicubebol and Related Sesquiterpenoids from the Brown Alga<i>Dictyopteris divaricata</i>
  作者：Minoru Suzuki、Nobuhiko Kowata、Etsuro Kurosawa

  DOI：10.1246/bcsj.54.2366

  日期：1981.8

  Epicubebol has been isolated from the methanol extracts of the brown alga Dictyopteris divaricata as the major constituent. Cadinane-type sesquiterpenes, cubebenes, δ-cadinene, cubenol, and epicubenol, as well as two sesquiterpene methyl ethers as minor constituents have also been obtained from the extracts.

  从褐藻 Dictyopteris divaricata 的甲醇提取物中分离出的主要成分是表贝酚。此外，还从萃取物中获得了笛烷类倍半萜、立方烯、δ-笛烷烯、立方醇和表贝醇，以及作为次要成分的两种倍半萜甲基醚。
• Gymnosperm nucleic acid molecules encoding sesquiterpene synthases and methods of use
  申请人：Washington State University Foundation

  公开号：US06265639B1

  公开（公告）日：2001-07-24

  cDNAs encoding E-&agr;-bisabolene synthase, &dgr;-selinene synthase and &ggr;-humulene synthase from Grand Fir (Abies grandis) have been isolated and sequenced, and the corresponding amino acid sequences have been determined. Accordingly, isolated DNA sequences (SEQ ID No:12 and SEQ ID No:19 and SEQ ID No:23) are provided which code for the expression of E-&agr;-bisabolene synthase (SEQ ID No:13), &dgr;-selinene synthase (SEQ ID No:20) and &ggr;-humulene synthase (SEQ ID No: 24), respectively, from Grand Fir (Abies grandis). In other aspects, replicable recombinant cloning vehicles are provided which code for E-&agr;-bisabolene synthase, &dgr;-selinene synthase and &ggr;-humulene synthase, or for a base sequence sufficiently complementary to at least a portion of E-&agr;-bisabolene synthase, &dgr;-selinene synthase or &ggr;-humulene synthase DNA or RNA to enable hybridization therewith. In yet other aspects, modified host cells are provided that have been transformed, transfected, infected and/or injected with a recombinant cloning vehicle and/or DNA sequence encoding E-&agr;-bisabolene synthase, &dgr;-selinene synthase or &ggr;-humulene synthase. Thus, systems and methods are provided for the recombinant expression of the aforementioned recombinant sesquiterpene synthases that may be used to facilitate their production, isolation and purification in significant amounts. Recombinant E-&agr;-bisabolene synthase, &dgr;-selinene synthase and &ggr;-humulene synthase may be used to obtain expression or enhanced expression of E-&agr;-bisabolene synthase, &dgr;-selinene synthase and &ggr;-humulene synthase in plants, or may be otherwise employed for the regulation or expression of E-&agr;-bisabolene synthase, &dgr;-selinene synthase and &ggr;-humulene synthase.

  已经分离和测序了来自大冷杉（Abies grandis）的编码E-α-藿烯合酶、δ-塞林烯合酶和γ-葎草烯合酶的cDNA，并确定了相应的氨基酸序列。因此，提供了编码来自大冷杉的E-α-藿烯合酶（SEQ ID No：13）、δ-塞林烯合酶（SEQ ID No：20）和γ-葎草烯合酶（SEQ ID No：24）表达的隔离DNA序列（SEQ ID No：12和SEQ ID No：19和SEQ ID No：23）。在其他方面，提供了可复制的重组克隆载体，其编码E-α-藿烯合酶、δ-塞林烯合酶和γ-葎草烯合酶，或者编码足够互补至少一部分E-α-藿烯合酶、δ-塞林烯合酶或γ-葎草烯合酶DNA或RNA的碱基序列，以使其能够与其杂交。在其他方面，提供了经过改造的宿主细胞，其已转化、转染、感染和/或注入重组克隆载体和/或编码E-α-藿烯合酶、δ-塞林烯合酶或γ-葎草烯合酶的DNA序列。因此，提供了用于重组表达前述重组倍半萜合酶的系统和方法，可用于促进其大量生产、分离和纯化。重组的E-α-藿烯合酶、δ-塞林烯合酶和γ-葎草烯合酶可用于在植物中获得E-α-藿烯合酶、δ-塞林烯合酶和γ-葎草烯合酶的表达或增强表达，或者可用于调节或表达E-α-藿烯合酶、δ-塞林烯合酶和γ-葎草烯合酶。
• Biochemical and Genomic Characterization of Terpene Synthases in<i>Magnolia grandiflora</i>     
  作者：Sungbeom Lee、Joseph Chappell

  DOI：10.1104/pp.108.115824

  日期：2008.7.8

  Magnolia grandiflora (Southern Magnolia) is a primitive evergreen tree that has attracted attention because of its horticultural distinctiveness, the wealth of natural products associated with it, and its evolutionary position as a basal angiosperm. Three cDNAs corresponding to terpene synthase (TPS) genes expressed in young leaves were isolated, and the corresponding enzymes were functionally characterized in vitro. Recombinant Mg25 converted farnesyl diphosphate (C15) predominantly to β-cubebene, while Mg17 converted geranyl diphosphate (C5) to α-terpineol. Efforts to functionally characterize Mg11 were unsuccessful. Transcript levels for all three genes were prominent in young leaf tissue and significantly elevated for Mg25 and Mg11 messenger RNAs in stamens. A putative amino-terminal signal peptide of Mg17 targeted the reporter green fluorescent protein to both chloroplasts and mitochondria when transiently expressed in epidermal cells of Nicotiana tabacum leaves. Phylogenetic analyses indicated that Mg25 and Mg11 belonged to the angiosperm sesquiterpene synthase subclass TPS-a, while Mg17 aligned more closely to the angiosperm monoterpene synthase subclass TPS-b. Unexpectedly, the intron-exon organizations for the three Magnolia TPS genes were different from one another and from other well-characterized TPS gene sets. The Mg17 gene consists of six introns arranged in a manner similar to many other angiosperm sesquiterpene synthases, but Mg11 contains only four introns, and Mg25 has only a single intron located near the 5′ terminus of the gene. Our results suggest that the structural diversity observed in the Magnolia TPS genes could have occurred either by a rapid loss of introns from a common ancestor TPS gene or by a gain of introns into an intron-deficient progenote TPS gene.

  大花玉兰（Southern Magnolia）是一种原始的常绿树，因其园艺特性、与之相关的丰富自然产物以及其作为基部被子植物的进化位置而受到关注。从年轻叶子中分离出了三个对应于萜类合成酶（TPS）基因的cDNA，并在体外对应的酶进行了功能特性化。重组Mg25主要将芬醇二磷酸（C15）转化为β-烯丙基苯，而Mg17将香叶醇二磷酸（C5）转化为α-萜芳醇。对Mg11进行功能特性化的努力没有成功。所有三个基因的转录本水平在年轻的叶组织中很突出，并且Mg25和Mg11信使RNA在雄蕊中显著升高。Mg17的一个推测的氨基端信号肽在暂时表达于烟草叶表皮细胞中时，将报告绿色荧光蛋白定位到叶绿体和线粒体中。系统发育分析表明，Mg25和Mg11属于被子植物倍半萜合成酶亚类TPS-a，而Mg17更接近于被子植物单萜合成酶亚类TPS-b。令人意外的是，这三个大花玉兰TPS基因的内含子 - 外显子组织结构彼此不同，也不同于其他经过充分特征化的TPS基因组。Mg17基因由6个内含子组成，排列方式类似于许多其他被子植物倍半萜合成酶，但是Mg11仅包含4个内含子，而Mg25仅有一个内含子位于基因的5'端附近。我们的结果表明，大花玉兰TPS基因的结构多样性可能是由于从共同祖先TPS基因中快速丢失内含子或将内含子增加到内含子缺乏的前体TPS基因中而发生的。

• Selectivity of Fungal Sesquiterpene Synthases: Role of the Active Site's H-1α Loop in Catalysis
  作者：Fernando López-Gallego、GraysonT. Wawrzyn、Claudia Schmidt-Dannert

  DOI：10.1128/aem.01811-10

  日期：2010.12

  Sesquiterpene synthases are responsible for the cyclization of farnesyl pyrophosphate into a myriad of structurally diverse compounds with various biological activities. We examine here the role of the conserved active site H-α1 loop in catalysis in three previously characterized fungal sesquiterpene synthases. The H-α1 loops of Cop3, Cop4, and Cop6 from Coprinus cinereus were altered by site-directed mutagenesis and the resultant product profiles were analyzed by gas chromatography-mass spectrometry and compared to the wild-type enzymes. In addition, we examine the effect of swapping the H-α1 loop from the promiscuous enzyme Cop4 with the more selective Cop6 and the effect of acidic or basic conditions on loop mutations in Cop4. Directed mutations of the H-α1 loop had a marked effect on the product profile of Cop3 and Cop4, while little to no change was shown in Cop6. Swapping of the Cop4 and Cop6 loops with one another was again shown to influence the product profile of Cop4, while the product profile of Cop6 remained identical to the wild-type enzyme. The loop mutations in Cop4 also implicate specific residues responsible for the pH sensitivity of the enzyme. These results affirm the role of the H-α1 loop in catalysis and provide a potential target to increase the product diversity of terpene synthases.

  摘要 倍半萜合酶负责将焦磷酸法呢基环化成具有各种生物活性的结构多样的化合物。我们在此研究了保守的活性位点 H-α1 环在三个先前表征的真菌倍半萜合成酶催化作用中的作用。Cop3、Cop4 和 Cop6 的 H-α1 环来自于 Coprinus cinereus 通过定点突变改变了这些酶的 H-α1 环，并用气相色谱-质谱法分析了所得到的产物图谱，并将其与野生型酶进行了比较。此外，我们还研究了将杂合酶 Cop4 的 H-α1 环与选择性更强的 Cop6 互换的效果，以及酸性或碱性条件对 Cop4 环突变的影响。H-α1 环的定向突变对 Cop3 和 Cop4 的产物特征有明显影响，而 Cop6 几乎没有变化。Cop4 和 Cop6 环路的相互交换再次证明会影响 Cop4 的产物特征，而 Cop6 的产物特征则与野生型酶保持一致。Cop4 的环突变还牵涉到负责该酶 pH 敏感性的特定残基。这些结果肯定了 H-α1 环在催化中的作用，并为增加萜烯合成酶的产物多样性提供了一个潜在的目标。