(-)-(4S,7R)-germacra-(1(10)E,5E)-dien-11-ol

• 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: (-)-(4S,7R)-germacra-(1(10)E,5E)-dien-11-ol
• 英文别名: Germacradienol；2-[(1R,2E,4S,7E)-4,8-dimethylcyclodeca-2,7-dien-1-yl]propan-2-ol
• 化学式: C₁₅H₂₆O
• 分子量: 222.371
• InChiKey: ZVZPKUXZGROCDB-IFRRKGDKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (-)-(4S,7R)-germacra-(1(10)E,5E)-dien-11-ol 生成 (1S,4aS)-1,4a-Dimethyl-1,2,3,4,4a,5,6,8a-octahydro-naphthalene 、 丙酮
  参考文献：
  名称：

  Geosmin Biosynthesis.Streptomyces coelicolor Germacradienol/Germacrene D 合酶将二磷酸法呢酯转化为土臭素

  摘要：

  土臭素是造成潮湿土壤特有气味的原因。由革兰氏阳性土壤细菌天蓝色链霉菌的 SCO6073 (SC9B1.20) 基因编码的重组germacradienol 合酶与法呢基二磷酸 (2, FPP) 在 Mg2+ 存在下孵育，得到 (4S,7R)-germacra 的混合物-1(10)E,5E-diene-11-ol (3) (74%), (-)-(7S)-germacrene D (4) (10%), geosmin (1) (13%), 和一种碳氢化合物，暂定为八烷 5 (3%) 的结构。[1,1-2H2]FPP (2a)、(1R)-[1-2H]-FPP (2b) 和 (1S)-[1-2H]-FPP (2c) 与重组细菌二烯醇合酶的单独孵育，以及 D2O 中的 FPP (2)，

  DOI：

  10.1021/ja062669x
• 作为产物：
  描述：

  farnesyl pyrophosphate 、 水 生成 (-)-(4S,7R)-germacra-(1(10)E,5E)-dien-11-ol 、 pyrophosphoric acid
  参考文献：
  名称：

  伴有土工生物合成的天蓝色链霉菌胚芽甲烯醇合酶的表达和机理分析。

  摘要：

  该PCR已用于从链霉菌A3（2）中扩增出2181 bp的ORF，命名为SC9B1.20（= SCO6073），编码726个氨基酸的蛋白，并在推导的氨基酸水平上显示出明显的序列相似性。已知的倍半萜合酶戊烯合酶的N-末端和C-末端一半。全长重组蛋白在大肠杆菌中高水平表达，并显示出催化法尼基二磷酸Mg（2+）依赖性转化为倍半萜烯醇（4S，7R）-germacra-1（10）E，5E-二烯11醇。酶促环化的ak（cat）为6.2 +/- 0.5 x 10（-3）s（-1），法呢基二磷酸的K（m）为62 +/- 8 nM。SC9B1的N末端（366个氨基酸）结构域的表达。20种蛋白质还提供了一个功能齐全的环化酶，可将法呢基二磷酸酯转化为相同的倍半萜烯醇，其k（cat）稍低，为3.2 +/- 0.4 x 10（-3）s（-1），k（m）大两倍。 115 +/- 14 nM。相反，表达的SC9B1.20

  DOI：

  10.1073/pnas.0337625100

文献信息

• Expression and mechanistic analysis of a germacradienol synthase from <i>Streptomyces coelicolor</i> implicated in geosmin biosynthesis
  作者：David E. Cane、Rory M. Watt

  DOI：10.1073/pnas.0337625100

  日期：2003.2.18

  The PCR has been used to amplify a 2,181-bp ORF from Streptomyces coelicolor A3(2), designated SC9B1.20 (= SCO6073), encoding a protein of 726 amino acids and showing significant sequence similarity at the deduced amino acid level in both the N-terminal and C-terminal halves to the known sesquiterpene synthase pentalenene synthase. The full-length recombinant protein was expressed at high levels in

  该PCR已用于从链霉菌A3（2）中扩增出2181 bp的ORF，命名为SC9B1.20（= SCO6073），编码726个氨基酸的蛋白，并在推导的氨基酸水平上显示出明显的序列相似性。已知的倍半萜合酶戊烯合酶的N-末端和C-末端一半。全长重组蛋白在大肠杆菌中高水平表达，并显示出催化法尼基二磷酸Mg（2+）依赖性转化为倍半萜烯醇（4S，7R）-germacra-1（10）E，5E-二烯11醇。酶促环化的ak（cat）为6.2 +/- 0.5 x 10（-3）s（-1），法呢基二磷酸的K（m）为62 +/- 8 nM。SC9B1的N末端（366个氨基酸）结构域的表达。20种蛋白质还提供了一个功能齐全的环化酶，可将法呢基二磷酸酯转化为相同的倍半萜烯醇，其k（cat）稍低，为3.2 +/- 0.4 x 10（-3）s（-1），k（m）大两倍。 115 +/- 14 nM。相反，表达的SC9B1.20
• PCR-targeted <i>Streptomyces</i> gene replacement identifies a protein domain needed for biosynthesis of the sesquiterpene soil odor geosmin
  作者：Bertolt Gust、Greg L. Challis、Kay Fowler、Tobias Kieser、Keith F. Chater

  DOI：10.1073/pnas.0337542100

  日期：2003.2.18

  Streptomycetes are high G+C Gram-positive, antibiotic-producing, mycelial soil bacteria. The 8.7-Mb Streptomyces coelicolor genome was previously sequenced by using an ordered library of Supercos-1 clones. Here, we describe an efficient procedure for creating precise gene replacements in the cosmid clones by using PCR targeting and λ-Red-mediated recombination. The cloned Streptomyces genes are replaced with a cassette containing a selectable antibiotic resistance and oriT _RK2 for efficient transfer to Streptomyces by RP4-mediated intergeneric conjugation. Supercos-1 does not replicate in Streptomyces , but the clones readily undergo double-crossover recombination, thus creating gene replacements. The antibiotic resistance cassettes are flanked by yeast FLP recombinase target sequences for removal of the antibiotic resistance and oriT _RK2 to generate unmarked, nonpolar mutations. The technique has been used successfully by >20 researchers to mutate around 100 Streptomyces genes. As an example, we describe its application to the discovery of a gene involved in the production of geosmin, the ubiquitous odor of soil. The gene, Sco6073 ( cyc2 ), codes for a protein with two sesquiterpene synthase domains, only one of which is required for geosmin biosynthesis, probably via a germacra-1 (10) E,5E -dien-11-ol intermediate generated by the sesquiterpene synthase from farnesyl pyrophosphate.

  链霉菌是高G+C革兰氏阳性的、产生抗生素的、菌丝状土壤细菌。先前使用Supercos-1克隆有序文库对8.7-Mb的链霉菌基因组进行了测序。在这里，我们描述了一种有效的程序，通过使用PCR定向和λ-Red介导的重组，在cosmid克隆中创建精确的基因替换。克隆的链霉菌基因被含有可选择的抗生素耐药性和oriT_RK2的引物替换，以便通过RP4介导的种间接合作用高效地转移到链霉菌中。Supercos-1不会在链霉菌中复制，但克隆体容易经历双交叉重组，从而创建基因替换。抗生素耐药性引物被酵母FLP重组酶靶序列包围，以去除抗生素耐药性和oriT_RK2，生成未标记的非极性突变。这种技术已被20多名研究人员成功地用于突变约100个链霉菌基因。例如，我们描述了其在发现参与土壤普遍气味geosmin产生的基因方面的应用。该基因Sco6073（cyc2）编码一个具有两个倍半萜合成酶结构域的蛋白质，其中只有一个结构域对于geosmin生物合成是必需的，可能通过来自法尼基焦磷酸的倍半萜合成酶产生的germacra-1（10）E,5E-dien-11-ol中间体实现。
• Geosmin Biosynthesis in Streptomyces avermitilis. Molecular Cloning, Expression, and Mechanistic Study of the Germacradienol/Geosmin Synthase
  作者：David E Cane、Xiaofei He、Seiji Kobayashi、Satoshi Ōmura、Haruo Ikeda

  DOI：10.1038/ja.2006.66

  日期：2006.8

  recombinant GeoA from either S. avermitilis or S. coelicolor A3(2) was incubated with nerolidyl diphosphate (8), only the acyclic elimination products beta3-farnesene (10), (Z)-alpha-farnesene (11), and (E)-alpha-farnesene (12) were formed, thereby ruling out nerolidyl diphosphate as an intermediate in the conversion of farnesyl diphosphate to geosmin, germacradienol, and germacrene D.

  Geosmin（1）是潮湿土壤的特有气味。革兰氏阳性土壤细菌阿维链霉菌可产生土臭素（1）以及其前体芽孢烯醇（3）。阿维链霉菌基因SAV2163（geoA）与编码胚芽甲酚/ geosmin合酶的天蓝色链霉菌A3（2）SCO6073基因极为相似。带有geoA缺失的阿维链霉菌突变体既不能产生胚芽甲酚（3），也不能产生土臭素（1）。通过将完整的geoA基因导入突变体，可以恢复两种化合物的生物合成。在Mg2 +存在下，由阿维链霉菌SAV2163基因编码的重组GeoA与法呢基二磷酸（2）孵育，得到（4S，7R）-germacra-1（10）E，5E-二烯-11-的混合物ol（3）（66％），（7S）-germacrene D（4）（24％），土臭素（1）（8％）和碳氢化合物，初步分配了八环素5（2％）的结构。如预期的那样，将这种胚芽甲烯醇/ geosmin合酶与[1,1-（2）H2] FPP（2a）一
• Mechanism and Stereochemistry of the Germacradienol/Germacrene D Synthase of <i>Streptomyces </i><i>c</i><i>oelicolor</i> A3(2)
  作者：Xiaofei He、David E. Cane

  DOI：10.1021/ja039929k

  日期：2004.3.1

  Incubation of farnesyl diphosphate (1, FPP) with recombinant germacradienol synthase from Streptomyces coelicolor A3(2) gave, in addition to (4S,7R)-germacra-1(10)E,5E-diene-11-ol (2), 15% of (-)-germacrene D (5). Incubations of [1,1-2H2]FPP (1a), (1R)-[1-2H]FPP (1b), and (1S)-[1-2H]FPP (1c) with germacradienol/germacrene D synthase and analysis of the resulting samples of germacradienol (2) and germacrene D (5) by a combination of 1H, 2H, and 13C NMR and mass spectrometry established that it is H-1si of FPP that is lost in the formation of germacradienol (2) and that undergoes 1,3-hydride transfer in the formation of (-)-germacrene D (5). The proportion of the two products was also sensitive to isotopic labeling, with cyclization of (1S)-[1-2H]FPP (1c) giving an increased proportion (35%) of 5. These results could be explained by a mechanism involving partitioning of a common helminthogermacradienyl cation intermediate 7.
• Sesquiterpene and other constituents of the liverwort Dumortiera hirsuta
  作者：Masao Toyota、Tatsuhiko Yoshida、Junko Matsunami、Yoshinori Asakawa

  DOI：10.1016/s0031-9422(96)00479-7

  日期：1997.1

  A new sesquiterpene and 13 known compounds were isolated from the ether extract of Dumortiera hirsuta. Their structures were established by spectral and chemical evidence and/or X-ray crystallographic analysis. The structure of the new compound was shown to be (4S, 6R)-2,7,10-bisbolatrien-4-ol. The absolute configuration of (4S, 7R)-germacra-1(10)E, SE-dien-11-ol was established by chemical degradation, although it has been reported previously on the basis of the comparison of the magnitude of optical rotation with that of a related known compound. The tentative structure of isomarchantin C has been reported previously, but it has now been established by X-ray crystallographic analysis. Copyright (C) 1996 Elsevier Science Ltd