(9β)-Pimara-7,15-diene | 140147-41-7

• 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: (9β)-Pimara-7,15-diene
• 英文别名: syn-pimara-7,15-diene；9beta-Pimara-7,15-diene；(2R,4aR,4bS,8aS)-2-ethenyl-2,4b,8,8-tetramethyl-3,4,4a,5,6,7,8a,9-octahydro-1H-phenanthrene
• CAS: 140147-41-7
• 化学式: C₂₀H₃₂
• 分子量: 272.474
• InChiKey: VCOVNILQQQZROK-PIKOESSRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  (9β)-Pimara-7,15-diene 、 氧气 、 1-Deoxy-1-(7,8-dimethyl-2,4-dioxidobenzo[g]pteridin-10(5H)-yl)-5-O-phosphonopentitol 生成 9beta-Pimara-7,15-dien-19-oate 、 氢(+1)阳离子 、 水 、 FMN
  参考文献：
  名称：

  CYP99A3：来自水稻莫米内酯生物合成基因簇的二萜氧化酶的功能鉴定。

  摘要：

  水稻（Oryza sativa）产生作为植物抗毒素和化感物质的莫米内酯二萜类化合物。引人注目的是，水稻基因组包含一个用于生产莫米内酯的生物合成基因簇，位于水稻 4 号染色体上，其中包含两个细胞色素 P450 (CYP) 单加氧酶，CYP99A2 和 CYP99A3，其作用未明确；尽管之前已经表明，这对密切相关的 CYP 的 RNA 干扰双敲低会减少莫米内酯的积累。在这里，我们尝试对 CYP99A2 和 CYP99A3 进行生化表征，最终通过完整的基因重新编码实现，从而在细菌中实现功能性重组表达。使用这些合成基因构建体可以证明，虽然 CYP99A2 对二萜底物没有表现出显着的活性，CYP99A3 催化莫米内酯前体 syn-pimaradien-7,15-diene 的 C19 甲基的连续氧化，依次形成 syn-pimaradien-19-ol、syn-pimaradien-19-al 和 s

  DOI：

  10.1111/j.1365-313x.2010.04408.x
• 作为产物：
  描述：

  (9β)-Pimara-7,15-dien-18-yl methanesulfonate 在 lithium-sodium alloy 、 氨 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 5.08h， 生成 (9β)-Pimara-7,15-diene
  参考文献：
  名称：

  Partial synthesis of 9,10-syn-diterpenes via tosylhydrazone reduction: (-)-(9.beta.)-pimara-7,15-diene and (-)-(9.beta.)-isopimaradiene

  摘要：

  (9-β)-坝沙烯-7,15-二烯(3)及其C-13表式异构体(4)是从水稻中产生的植保素类木菠萝烯(1和2)生物合成中的一个中间体。3和4从甲基巴沙和异巴沙-8,15-二烯-18酸(8b和8a)中合成。铬酸-二吡啶配合物对8a和8b以及它们的二烯烃15a和15b进行邻位氧化得到8,15-二烯-7-酮类化合物-9a、9b、16a和16b(35-54%产率)。用液氨-锂对9a、16a和16b进行还原,主要产率获得trans,anti,trans-异巴沙和巴沙-15-烯-7-酮(10,17a和17b)。相比之下,使用邻苯二酚硼烷还原9a和9b的犀角腙,得到具有9,10-顺式立体结构的甲基(9-β)-异巴沙-7,15-二烯-20酸和甲基(9-β)-巴沙-7,15-二烯-20酸(23a和23b)。通过羧酸基团转化为甲基基团得到这两种二烯烃的亲本化合物。合作研究发现,3是用紫外处理过的水稻粗酶提取液培养(E,E,E)-瑞香龙脑二磷酸酯后产生的五种二烯烃中的一种。

  DOI：

  10.1021/jo00043a013

文献信息

• Biological functions of <i>ent</i>‐ and <i>syn</i>‐copalyl diphosphate synthases in rice: key enzymes for the branch point of gibberellin and phytoalexin biosynthesis
  作者：Kazuko Otomo、Hiromichi Kenmoku、Hideaki Oikawa、Wilfried A. König、Hiroaki Toshima、Wataru Mitsuhashi、Hisakazu Yamane、Takeshi Sassa、Tomonobu Toyomasu

  DOI：10.1111/j.1365-313x.2004.02175.x

  日期：2004.9

  Rice (Oryza sativa L.) produces ent‐copalyl diphosphate (ent‐CDP) and syn‐CDP as precursors for several classes of phytoalexins and the phytohormones, gibberellins (GAs). It has recently been shown that a loss‐of‐function mutation of OsCPS1, a gene encoding a putative ent‐CDP synthase, results in a severely GA‐deficient dwarf phenotype in rice. To clarify the biological functions of the ent‐ and syn‐CDP synthases involved in the biosynthesis of phytoalexins and/or GAs, we isolated two cDNAs, OsCyc1 and OsCyc2, encoding putative diterpene cyclases from ultraviolet (UV)‐irradiated rice leaves (cv. Nipponbare). The production of phytoalexins in rice leaves is known to be highly induced by UV treatment. Using a bacterial expression system, we demonstrated that OsCyc1 encodes syn‐CDP synthase and that OsCyc2 and OsCPS1 encode ent‐CDP synthase. The level of expression of the OsCyc1 and OsCyc2 transcripts in rice leaves increased drastically in response to UV treatment, whereas expression of the OsCPS1 transcript was not induced by UV light. These results suggest that OsCyc1, OsCyc2 and OsCPS1 are responsible for the biosynthesis of momilactones A and B and oryzalexin S, oryzalexins A–F and phytocassanes A–E, and GAs, respectively. Our results strongly suggest the presence of two ent‐CDP synthase isoforms in rice, one that participates in the biosynthesis of GAs and a second that is involved in the biosynthesis of phytoalexins.

  摘要水稻（Oryza sativa L.）产生ent-copalyl diphosphate（ent-CDP）和syn-CDP，作为几类植物素和植物激素赤霉素（GA）的前体。最近的研究表明，编码推测的ent-CDP合成酶的基因OsCPS1发生功能缺失突变，会导致水稻出现严重的GA缺陷性矮小表型。为了弄清参与植物雌激素和/或 GA 生物合成的ent-和 syn-CDP 合成酶的生物学功能，我们从紫外线（UV）照射的水稻（cv. Nipponbare）叶片中分离出了两个 cDNA，即编码假定二萜环化酶的 OsCyc1 和 OsCyc2。众所周知，紫外线处理会高度诱导水稻叶片中植物烯酮素的产生。利用细菌表达系统，我们证明 OsCyc1 编码 syn-CDP 合成酶，OsCyc2 和 OsCPS1 编码 ent-CDP 合成酶。在紫外线处理下，水稻叶片中 OsCyc1 和 OsCyc2 转录本的表达水平急剧上升，而 OsCPS1 转录本的表达不受紫外线诱导。这些结果表明，OsCyc1、OsCyc2 和 OsCPS1 分别负责莫米内酯 A 和 B、橙皮苷 S、橙皮苷 A-F 和植物鞣剂 A-E 以及 GAs 的生物合成。我们的研究结果有力地证明了水稻中存在两种 ent-CDP 合成酶同工酶，一种参与 GA 的生物合成，另一种参与植物雌激素的生物合成。
• Identification of <i>Syn</i>-Pimara-7,15-Diene Synthase Reveals Functional Clustering of Terpene Synthases Involved in Rice Phytoalexin/Allelochemical Biosynthesis
  作者：P. Ross Wilderman、Meimei Xu、Yinghua Jin、Robert M. Coates、Reuben J. Peters

  DOI：10.1104/pp.104.045971

  日期：2004.8.1

  Rice (Oryza sativa) produces momilactone diterpenoids as both phytoalexins and allelochemicals. Accordingly, the committed step in biosynthesis of these natural products is catalyzed by the class I terpene synthase that converts syn-copalyl diphosphate to the corresponding polycyclic hydrocarbon intermediate syn-pimara-7,15-diene. Here, a functional genomics approach was utilized to identify a syn-copalyl diphosphate specific 9β-pimara-7,15-diene synthase (OsDTS2). To our knowledge, this is the first identified terpene synthase with this particular substrate stereoselectivity and, by comparison with the previously described and closely related ent-copalyl diphosphate specific cassa-12,15-diene synthase (OsDTC1), provides a model system for investigating the enzymatic determinants underlying the observed difference in substrate specificity. Further, OsDTS2 mRNA in leaves is up-regulated by conditions that stimulate phytoalexin biosynthesis but is constitutively expressed in roots, where momilactones are constantly synthesized as allelochemicals. Therefore, transcription of OsDTS2 seems to be an important regulatory point for controlling production of these defensive compounds. Finally, the gene identified here as OsDTS2 has previously been mapped at 14.3 cM on chromosome 4. The class II terpene synthase producing syn-copalyl diphosphate from the universal diterpenoid precursor geranylgeranyl diphosphate was also mapped to this same region. These genes catalyze sequential cyclization steps in momilactone biosynthesis and seem to have been evolutionarily coupled by physical linkage and resulting cosegregation. Further, the observed correlation between physical proximity and common metabolic function indicates that other such class I and class II terpene synthase gene clusters may similarly catalyze consecutive reactions in shared biosynthetic pathways.

  水稻（Oryza sativa）产生莫米松二萜作为植物保护素和化感物质。因此，这些天然产物生物合成的承诺步骤由一类萜烯合酶催化，将syn-茄榄烯二磷酸酯转化为相应的多环烃中间体syn-哌麻烷-7,15-二烯。本研究采用功能基因组学方法鉴定了一种syn-茄榄烯二磷酸酯特异性的9β-哌麻烷-7,15-二烯合酶（OsDTS2）。据我们所知，这是第一个具有这种底物立体选择性的萜烯合酶，并与先前描述的密切相关的ent-茄榄烯二磷酸酯特异性cassa-12,15-二烯合酶（OsDTC1）进行比较，为研究底物特异性的酶学决定因素提供了一个模型系统。此外，叶中的OsDTS2 mRNA在刺激植物保护素生物合成的条件下被上调，但在根中被恒定地表达，其中莫米松作为化感物质不断被合成。因此，OsDTS2的转录似乎是控制这些防御化合物产生的重要调节点。最后，在这里鉴定的基因OsDTS2以前已被定位在第4染色体的14.3 cM处。产生syn-茄榄烯二磷酸酯的第二类萜烯合酶从万能二萜类前体青蒿烯二磷酸酯中催化，也被映射到同一区域。这些基因在莫米松生物合成中催化顺序环化步骤，并似乎通过物理连锁和结果共分离而进化耦合。此外，物理接近和共同代谢功能之间的观察到的相关性表明，其他类似的一类和二类萜烯合酶基因簇可能同样在共享的生物合成途径中催化连续反应。

• Diterpene Cyclases Responsible for the Biosynthesis of Phytoalexins, Momilactones A, B, and Oryzalexins A–F in Rice
  作者：Kazuko OTOMO、Yuri KANNO、Akihiro MOTEGI、Hiromichi KENMOKU、Hisakazu YAMANE、Wataru MITSUHASHI、Hideaki OIKAWA、Hiroaki TOSHIMA、Hironori ITOH、Makoto MATSUOKA、Takeshi SASSA、Tomonobu TOYOMASU

  DOI：10.1271/bbb.68.2001

  日期：2004.1

  sativa L.) produces diterpene phytoalexins, such as momilactones, oryzalexins, and phytocassanes. Using rice genome information and in vitro assay with recombinant enzymes, we identified genes (OsKS4 and OsKS10) encoding the type-A diterpene cyclases 9beta-pimara-7,15-diene synthase and ent-sandaracopimaradiene synthase which are involved in the biosynthesis of momilactones A, B and oryzalexins A-F

  水稻（Oryza sativa L.）产生二萜植物抗毒素，例如妈咪内酯，稻谷新解毒素和植物酪蛋白。利用水稻基因组信息并利用重组酶进行体外测定，我们鉴定了编码A型二萜环化酶9beta-pimara-7,15-二烯合酶和对-砂仁花生红素合酶的基因（OsKS4和OsKS10），它们参与了母乳内酯的生物合成。 A，B和稻米黄素AF。紫外线（UV）处理后，这两个基因的转录水平显着增加，这与紫外线引起的植物抗毒素的产生一致。这两个基因可能证明是了解水稻植物防御机制的有力工具。
• Characterization of CYP76M5–8 Indicates Metabolic Plasticity within a Plant Biosynthetic Gene Cluster
  作者：Qiang Wang、Matthew L. Hillwig、Kazunori Okada、Kohei Yamazaki、Yisheng Wu、Sivakumar Swaminathan、Hisakazu Yamane、Reuben J. Peters

  DOI：10.1074/jbc.m111.305599

  日期：2012.2

  Intriguingly, the preceding diterpene synthase for oryzalexin biosynthesis, unlike that for the phytocassanes, is not found in the chromosome 2 diterpenoid biosynthetic gene cluster. Accordingly, our results not only uncover a complex evolutionary history, but also further suggest some intriguing differences between plant biosynthetic gene clusters and the seemingly similar microbial operons. The implications

  最近的报告揭示了植物专门/次级代谢中特定生物合成途径的酶基因的基因组聚类。水稻（Oryza sativa）携带两个这样的簇用于生产抗菌二萜类植物抗毒素，2 号染色体上的簇包含细胞色素 P450 CYP76M 亚家族（CYP76M5-8）的四个密切相关/同源成员。值得注意的是，这些 CYP 的潜在进化扩展似乎发生在祖先生物合成基因簇组装之后，表明它们具有不同的作用。已经证明 CYP76M7 催化 ent-cassadiene 的 C11α-羟基化，并可能介导衍生的植物卡桑类植物抗毒素生物合成的早期步骤。在这里，我们报告了 CYP76M5、-6 和 -8 的生化特征。我们的结果表明 CYP76M8 是一种多功能/混杂的羟化酶，与 CYP76M8 相比，CYP76M5 和 -7 似乎仅提供多余的活性，而 CYP76M6 似乎提供多余的和新的活性。RNAi 介导的 CYP76M7 和 -8 双重敲
• Optimization of recombinant expression enables discovery of novel cytochrome P450 activity in rice diterpenoid biosynthesis
  作者：Naoki Kitaoka、Yisheng Wu、Meimei Xu、Reuben J. Peters

  DOI：10.1007/s00253-015-6496-2

  日期：2015.9

  The oxygenation reactions catalyzed by cytochromes P450 (CYPs) play critical roles in plant natural products biosynthesis. At the same time, CYPs are one of most challenging enzymes to functionally characterize due to the difficulty of recombinantly expressing these membrane-associated monooxygenases. In the course of investigating rice diterpenoid biosynthesis, we have developed a synthetic biology approach for functional expression of relevant CYPs in Escherichia coli. In certain cases, activity was observed for only one of two closely related paralogs although it seems clear that related reactions are required for production of the known diterpenoids. Here, we report that optimization of the recombinant expression system enabled characterization of not only these previously recalcitrant CYPs, but also discovery of additional activity relevant to rice diterpenoid biosynthesis. Of particular interest, CYP701A8 was found to catalyze 3 beta-hydroxylation of syn-pimaradiene, which is presumably relevant to momilactone biosynthesis, while CYP71Z6 & 7 were found to catalyze multiple reactions, with CYP71Z6 catalyzing the production of 2 alpha,3 alpha-dihydroxy-ent-isokaurene via 2 alpha-hydroxy-ent-isokaurene, and CYP71Z7 catalyzing the production of 3 alpha-hydroxy-ent-cassadien-2-one via 2 alpha-hydroxy-ent-cassadiene and ent-cassadien-2-one, which may be relevant to oryzadione and phytocassane biosynthesis, respectively.