Germacra-1(10),4,11(13)-trien-12-al | 88719-08-8

• 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: Germacra-1(10),4,11(13)-trien-12-al
• 英文别名: 2-[(1R,3E,7E)-4,8-dimethylcyclodeca-3,7-dien-1-yl]prop-2-enal
• CAS: 88719-08-8
• 化学式: C₁₅H₂₂O
• 分子量: 218.33
• InChiKey: AXUADEXBLHHYAJ-KGSGWQTPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Germacra-1(10),4,11(13)-trien-12-al 、 水 、 NADP⁺ 生成 Germacra-1(10),4,11(13)-trien-12-oate 、 氢(+1)阳离子 、 NADPH(4-)
  参考文献：
  名称：

  菊苣根中Germacrene A 羧酸的生物合成。细胞色素 P450 (+)-germacrene、羟化酶和 NADP+ 依赖性倍半萜脱氢酶参与倍半萜内酯生物合成的演示。

  摘要：

  菊苣芽（Cichorium intybus）是一种在黑暗中生长的蔬菜，其味道略带苦味，与愈创木酚内酯、eudesmanolides 和 Germacranolides 的存在有关。这些化合物生物合成的关键步骤是由 (+)-germacrene A 合酶催化的。内酯环的形成是假设的衍生于锗烯的倍半萜内酯生物合成的下一步。本研究通过从菊苣根中分离酶活性证实了这一假设，该酶活性在germacrene A异丙烯基侧链中引入了羧酸功能，这对于内酯环的形成是必需的。 (+)-germacrene A 通过细胞色素 P450 酶羟基化为 germacra-1(10),4,11(13)-trien-12-ol，随后氧化为 germacra-1(10),4,11( 13)-trien-12-oic 酸通过 NADP+ 依赖性脱氢酶产生。两种氧化的锗烯均被检测为它们的 Cope 重排产物 elema-1,3,11(13)-trien-12-ol

  DOI：

  10.1104/pp.125.4.1930
• 作为产物：
  描述：

  Germacra-1(10),4,11(13)-trien-12-ol 、 NADP⁺ 生成 Germacra-1(10),4,11(13)-trien-12-al 、 氢(+1)阳离子 、 NADPH(4-)
  参考文献：
  名称：

  菊苣根中Germacrene A 羧酸的生物合成。细胞色素 P450 (+)-germacrene、羟化酶和 NADP+ 依赖性倍半萜脱氢酶参与倍半萜内酯生物合成的演示。

  摘要：

  菊苣芽（Cichorium intybus）是一种在黑暗中生长的蔬菜，其味道略带苦味，与愈创木酚内酯、eudesmanolides 和 Germacranolides 的存在有关。这些化合物生物合成的关键步骤是由 (+)-germacrene A 合酶催化的。内酯环的形成是假设的衍生于锗烯的倍半萜内酯生物合成的下一步。本研究通过从菊苣根中分离酶活性证实了这一假设，该酶活性在germacrene A异丙烯基侧链中引入了羧酸功能，这对于内酯环的形成是必需的。 (+)-germacrene A 通过细胞色素 P450 酶羟基化为 germacra-1(10),4,11(13)-trien-12-ol，随后氧化为 germacra-1(10),4,11( 13)-trien-12-oic 酸通过 NADP+ 依赖性脱氢酶产生。两种氧化的锗烯均被检测为它们的 Cope 重排产物 elema-1,3,11(13)-trien-12-ol

  DOI：

  10.1104/pp.125.4.1930

文献信息

• Plant enzymes for bioconversion
  申请人：Bouwmeester Jan Hendrik

  公开号：US20050019882A1

  公开（公告）日：2005-01-27

  The invention provides the use of enzymes derived from plants in biocatalysis. The regio- and stercoselective introduction of an oxygen group into an unactivated organic compound is still a largely unresolved challenge to organic chemistry (Faber, 2000). We have shown that enzymes of Asteraceae species are capable of converting with high regio- and stereospecificity for example sesquiterpene olefins to commercially interesting products.

  本发明提供了植物来源酶在生物催化中的应用。将氧基引入未活化有机化合物中的区域和立体选择性仍然是有机化学中一个基本未解决的挑战（Faber，2000）。我们已经证明，菊科物种的酶能够高度区域和立体特异性地将倍半萜烯烃等转化为商业上有趣的产物。
• Biosynthesis of Germacrene A Carboxylic Acid in Chicory Roots. Demonstration of a Cytochrome P450 (+)-Germacrene A Hydroxylase and NADP+-Dependent Sesquiterpenoid Dehydrogenase(s) Involved in Sesquiterpene Lactone Biosynthesis
  作者：Jan-Willem de Kraker、Maurice C. R. Franssen、Marcella C. F. Dalm、Aede de Groot、Harro J. Bouwmeester

  DOI：10.1104/pp.125.4.1930

  日期：2001.4.1

  Sprouts of chicory (Cichorium intybus), a vegetable grown in the dark, have a slightly bitter taste associated with the presence of guaianolides, eudesmanolides, and germacranolides. The committed step in the biosynthesis of these compounds is catalyzed by a (+)-germacrene A synthase. Formation of the lactone ring is the postulated next step in biosynthesis of the germacrene-derived sesquiterpene lactones

  菊苣芽（Cichorium intybus）是一种在黑暗中生长的蔬菜，其味道略带苦味，与愈创木酚内酯、eudesmanolides 和 Germacranolides 的存在有关。这些化合物生物合成的关键步骤是由 (+)-germacrene A 合酶催化的。内酯环的形成是假设的衍生于锗烯的倍半萜内酯生物合成的下一步。本研究通过从菊苣根中分离酶活性证实了这一假设，该酶活性在germacrene A异丙烯基侧链中引入了羧酸功能，这对于内酯环的形成是必需的。 (+)-germacrene A 通过细胞色素 P450 酶羟基化为 germacra-1(10),4,11(13)-trien-12-ol，随后氧化为 germacra-1(10),4,11( 13)-trien-12-oic 酸通过 NADP+ 依赖性脱氢酶产生。两种氧化的锗烯均被检测为它们的 Cope 重排产物 elema-1,3,11(13)-trien-12-ol
• Elucidation and in planta reconstitution of the parthenolide biosynthetic pathway
  作者：Qing Liu、David Manzano、Nikola Tanić、Milica Pesic、Jasna Bankovic、Irini Pateraki、Lea Ricard、Albert Ferrer、Ric de Vos、Sander van de Krol、Harro Bouwmeester

  DOI：10.1016/j.ymben.2014.03.005

  日期：2014.5

  Parthenolide, the main bioactive compound of the medicinal plant feverfew (Tanacetum parthenium), is a promising anti-cancer drug. However, the biosynthetic pathway of parthenolide has not been elucidated yet. Here we report on the isolation and characterization of all the genes from feverfew that are required for the biosynthesis of parthenolide, using a combination of 454 sequencing of a feverfew glandular trichome cDNA library, co-expression analysis and metabolomics. When parthenolide biosynthesis was reconstituted by transient co-expression of all pathway genes in Nicotiana benthamiana, up to 1.4 mu g g(-1) parthenolide was produced, mostly present as cysteine and glutathione conjugates. These relatively polar conjugates were highly active against colon cancer cells, with only slightly lower activity than free parthenolide. In addition to these biosynthetic genes, another gene encoding a costunolide and parthenolide 3 beta-hydroxylase was identified opening up further options to improve the water solubility of parthenolide and therefore its potential as a drug. (C) 2014 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.
• US7214507B2
  申请人：——

  公开号：US7214507B2

  公开（公告）日：2007-05-08
• Biochemical Conservation and Evolution of Germacrene A Oxidase in Asteraceae
  作者：Don Trinh Nguyen、Jens Christian Göpfert、Nobuhiro Ikezawa、Gillian MacNevin、Meena Kathiresan、Jürgen Conrad、Otmar Spring、Dae-Kyun Ro

  DOI：10.1074/jbc.m110.111757

  日期：2010.5

  Sesquiterpene lactones are characteristic natural products in Asteraceae, which constitutes similar to 8% of all plant species. Despite their physiological and pharmaceutical importance, the biochemistry and evolution of sesquiterpene lactones remain unexplored. Here we show that germacrene A oxidase (GAO), evolutionarily conserved in all major subfamilies of Asteraceae, catalyzes three consecutive oxidations of germacrene A to yield germacrene A acid. Furthermore, it is also capable of oxidizing non-natural substrate amorphadiene. Co-expression of lettuce GAO with germacrene synthase in engineered yeast synthesized aberrant products, costic acids and ilicic acid, in an acidic condition. However, cultivation in a neutral condition allowed the de novo synthesis of a single novel compound that was identified as germacrene A acid by gas and liquid chromatography and NMR analyses. To trace the evolutionary lineage of GAO in Asteraceae, homologous genes were further isolated from the representative species of three major subfamilies of Asteraceae (sunflower, chicory, and costus from Asteroideae, Cichorioideae, and Carduoideae, respectively) and also from the phylogenetically basal species, Barnadesia spinosa, from Barnadesioideae. The recombinant GAOs from these genes clearly showed germacrene A oxidase activities, suggesting that GAO activity is widely conserved in Asteraceae including the basal lineage. All GAOs could catalyze the three-step oxidation of non-natural substrate amorphadiene to artemisinic acid, whereas amorphadiene oxidase diverged from GAO displayed negligible activity for germacrene A oxidation. The observed amorphadiene oxidase activity in GAOs suggests that the catalytic plasticity is embedded in ancestral GAO enzymes that may contribute to the chemical and catalytic diversity in nature.