(1RS,4aS,7S,7aR)-Nepetalactol | 109215-55-6

• 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: (1RS,4aS,7S,7aR)-Nepetalactol
• 英文别名: nepetalactol；(4aS,7S,7aR)-4,7-dimethyl-1,4a,5,6,7,7a-hexahydrocyclopenta[c]pyran-1-ol
• CAS: 109215-55-6
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: OJGPEAXUHQRLNC-CEPLBNANSA-N

物化性质

• 沸点：
  267.1±29.0 °C(Predicted)
• 密度：
  1.051±0.06 g/cm3(Predicted)
• 溶解度：
  可溶于DMSO（少许）、甲醇（少许）

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1RS,4aS,7S,7aR)-Nepetalactol 在 重铬酸吡啶 、 4 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 以33%的产率得到假荆芥内酯
  参考文献：
  名称：

  Kigawa, Masaharu; Tanaka, Masahide; Mitsuhashi, Hiroshi, Heterocycles, 1992, vol. 33, # 1, p. 117 - 120

  摘要：

  DOI：
• 作为产物：
  描述：

  (S)-(-)-β-香茅醇 在 叔丁基过氧化氢 、 selenium(IV) oxide 、 pyridine-SO3 complex 、 4 A molecular sieve 、 水 、 对甲苯磺酸 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 异辛烷 、 乙醚 、 二氯甲烷 为溶剂， 反应 74.0h， 生成 (1RS,4aS,7S,7aR)-Nepetalactol
  参考文献：
  名称：

  The aphid sex pheromone cyclopentanoids: Synthesis in the elucidation of structure and biosynthetic pathways

  摘要：

  Identification of a range of aphid sex pheromones as comprising the cyclopentanoids (4aS,7S,7aR)-nepetalactune, (1R,4aS,7S,7aR)-nepetalactol and the (1S)- and (1R,4aR,7S,7aS)-nepetalactols required samples authenticated by H-1 and C-13 NMR. These and related compounds were provided by small scale synthesis and extraction from plants in the genus Nepeta (Lamiaceae). The subsequent discovery that the synthetic sex pheromones could attract males, and also parasitic wasps that attack aphids, has created a need for large scale syntheses of the cyclopentanoids. This is afforded by cyclisation of the 8-oxo-1-enamine of citronellal as originally developed by Schreiber and co-workers (1986). Investigation into the biosynthesis of the cyclopentanoids by plants for exploiting aphid sex pheromones in crop protection by means of molecular biology required synthesis of putative biosynthetic intermediates, some with radioactive isotopic labelling, particularly 8-oxidised monoterpene alcohols and aldehydes. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0968-0896(96)00012-0

文献信息

• An alternative route to cyclic terpenes by reductive cyclization in iridoid biosynthesis
  作者：Fernando Geu-Flores、Nathaniel H. Sherden、Vincent Courdavault、Vincent Burlat、Weslee S. Glenn、Cen Wu、Ezekiel Nims、Yuehua Cui、Sarah E. O’Connor

  DOI：10.1038/nature11692

  日期：2012.12

  Iridoids are a large family of bicyclic natural products that possess anticancer, anti-inflammatory, antifungal and antibacterial activities; here the essential cyclization step in their biosynthesis is identified, opening up the possibility of production of naturally occurring and synthetic variants of iridoids for use in pharmacy or agriculture. This paper reports the identification of iridoid synthase, a key enzyme in the biosynthesis of iridoids, a large family of bicyclic natural products that possess anticancer, anti-inflammatory, antifungal and antibacterial activities. The enzyme produces a bicyclic ring system via a novel NAD(P)H-dependent cascade reaction. Knowledge of its structure and function should contribute towards efforts aimed at modifying and reconstituting iridoid and related pathways in crop plants or microbes for agricultural and pharmaceutical purposes. The iridoids comprise a large family of distinctive bicyclic monoterpenes that possess a wide range of pharmacological activities, including anticancer, anti-inflammatory, antifungal and antibacterial activities1,2,3,4. Additionally, certain iridoids are used as sex pheromones in agriculturally important species of aphids, a fact that has underpinned innovative and integrated pest management strategies5. To harness the biotechnological potential of this natural product class, the enzymes involved in the biosynthetic pathway must be elucidated. Here we report the discovery of iridoid synthase, a plant-derived enzyme that generates the iridoid ring scaffold, as evidenced by biochemical assays, gene silencing, co-expression analysis and localization studies. In contrast to all known monoterpene cyclases, which use geranyl diphosphate as substrate and invoke a cationic intermediate, iridoid synthase uses the linear monoterpene 10-oxogeranial as substrate and probably couples an initial NAD(P)H-dependent reduction step with a subsequent cyclization step via a Diels–Alder cycloaddition or a Michael addition. Our results illustrate how a short-chain reductase was recruited as cyclase for the production of iridoids in medicinal plants. Furthermore, we highlight the prospects of using unrelated reductases to generate artificial cyclic scaffolds. Beyond the recognition of an alternative biochemical mechanism for the biosynthesis of cyclic terpenes, we anticipate that our work will enable the large-scale heterologous production of iridoids in plants and microorganisms for agricultural5,6,7,8 and pharmaceutical1,2,3,4,9 applications.

  铱类化合物是一大类双环天然产物，具有抗癌、消炎、抗真菌和抗菌活性；本文鉴定了其生物合成过程中的关键环化步骤，为生产天然存在和合成的铱类化合物变体用于制药或农业提供了可能性。虹彩类化合物是一大类具有抗癌、消炎、抗真菌和抗菌活性的双环天然产物，本文报告了对虹彩合成酶的鉴定，这是虹彩类化合物生物合成过程中的一种关键酶。该酶通过一种新型的 NAD(P)H 依赖性级联反应生成双环系统。对其结构和功能的了解将有助于为农业和制药目的而改造和重建作物植物或微生物中的铱类化合物及相关途径。虹彩类化合物由一大类独特的双环单萜组成，具有广泛的药理活性，包括抗癌、抗炎、抗真菌和抗菌活性1,2,3,4。此外，某些虹彩类物质还被用作农业上重要的蚜虫物种的性信息素，这一事实为创新性虫害综合防治策略提供了基础5。要利用这一类天然产品的生物技术潜力，必须阐明生物合成途径中涉及的酶。在此，我们报告了鸢尾甙合成酶的发现，这是一种产生鸢尾甙环支架的植物源酶，生化测定、基因沉默、共表达分析和定位研究都证明了这一点。所有已知的单萜烯环化酶都使用二磷酸香叶酯作为底物并调用阳离子中间体，与此不同的是，鸢尾环合成酶使用线性单萜烯 10-oxogeranial 作为底物，并可能通过 DielsâAlder 环加成或迈克尔加成将最初的 NAD(P)H 依赖性还原步骤与随后的环化步骤结合起来。我们的研究结果说明了药用植物中的短链还原酶是如何作为环化酶用于生产虹彩类化合物的。此外，我们还强调了使用不相关的还原酶生成人工环状支架的前景。除了认识到环状萜类化合物生物合成的另一种生化机制之外，我们还预计我们的工作将使植物和微生物能够大规模异源生产虹彩类化合物，用于农业5,6,7,8 和医药1,2,3,4,9 应用。
• Dynamics of loops at the substrate entry channel determine the specificity of iridoid synthases
  作者：Anand S. Sandholu、Madhura Mohole、William L. Duax、Hirekodathakallu V. Thulasiram、Durba Sengupta、Kiran Kulkarni

  DOI：10.1002/1873-3468.13174

  日期：2018.8

  Iridoid synthases belong to the family of short‐chain dehydrogenase/reductase involved in the biosynthesis of iridoids. Despite having high sequence and structural homology with progesterone 5β‐reductase, these enzymes exhibit differential substrate specificities. Previously, two loops, L1 and L2 at substrate‐binding pocket, were suggested to be involved in generating substrate specificity. However

  环烯醚萜合酶属于参与环烯醚萜生物合成的短链脱氢酶/还原酶家族。尽管与孕酮 5β-还原酶具有高度的序列和结构同源性，但这些酶表现出不同的底物特异性。以前，底物结合口袋中的两个环，L1 和 L2，被认为与产生底物特异性有关。然而，特异性决定因素的结构基础是难以捉摸的。在这里，结合序列和结构分析、定点诱变和分子动力学模拟，我们已经证明环烯醚萜合酶包含两个底物进入通道，其几何形状被 L1-L2 动力学改变，主要由残基 Glu161 和 Gly162 的相互作用协调。 L2 的 L1 和 Asn358。
• ——
  作者：A. M. Hooper、B. Donato、C. M. Woodcock、J. H. Park、R. L. Paul、K. S. Boo、J. Hardie、J. A. Pickett

  DOI：10.1023/a:1015201129331

  日期：——

  the main constituent of the essential oil of the catmint plant Nepeta cataria. The stereochemistry of the compounds was determined by NMR spectroscopy and X-ray crystallography, and the compounds were identified, respectively, as neomatatabiol and isoneomatatabiol, natural products from Actinidia polygama, for which the lactol stereochemistry was previously incompletely defined. Compound 1 was found

  对映体纯的非对映异构体（1R，4S，4aR，7S，7aR）-（1）和（1R，4R，4aR，7S，7aR）-二氢荆芥内酯（2）由可再生资源（4aS，7S，7aR）非对映选择性合成）-荆芥内酯（3），被分离为薄荷植物荆芥属的荆芥精油的主要成分。通过NMR光谱法和X射线晶体学测定化合物的立体化学，并且将化合物分别鉴定为来自松果猕猴桃（Actinidia polygama）的天然产物新matatabiol和isoonetmatatabiol，之前对乳糖醇的立体化学还没有完全定义。在韩国，发现化合物1在该领域捕获了大量的三种lace虫。Chrysopa cognata，以及在英国的Nineta vittata，最著名的是Peverimhoffina gracilis。在释放1的陷阱中发现的所有物种数量都比2更为频繁，而在释放（1R，4aS，7S，7aR）-荆芥内酯的陷阱中发现了更多的白兰地衣，C。formosa和C
• Nepetalactol oxidoreductase in trichomes of the catmint Nepeta racemosa
  作者：David L. Hallahan、Jevon M. West、Diane W.M. Smiley、John A. Pickett

  DOI：10.1016/s0031-9422(98)00006-5

  日期：1998.6

  Abstract Isomers of (7 S )-nepetalactone are the principal constituents of the essential oil accumulated by plants of the genus Nepeta (catmints), with the cis , cis -isomer predominating in the catmint N. racemosa . An enzyme which catalyses the NAD + -dependent oxidation of cis , cis -nepetalactol to cis , cis -nepetalactone has been identified in cell-free extracts of N. racemosa leaves. This enzyme

  摘要 (7 S )-荆芥内酯的异构体是荆芥属植物（荆芥）积累的精油的主要成分，在荆芥总状荆芥中以顺式、顺式异构体为主。已在总状花椰菜叶的无细胞提取物中鉴定出一种酶，该酶催化 NAD + 依赖性氧化顺式，顺式 - 荆芥内酯为顺式，顺式 - 荆芥内酯。这种酶已被部分纯化，并已被证明位于该物种叶子表面的毛状体中。因为腺毛已被证明是荆芥内酯在总状花序草和卡塔利亚山楂中积累的场所，毛状体中存在这种活性表明荆芥内酯可能是荆芥内酯生物合成的中间体。
• Uncoupled activation and cyclization in catmint reductive terpenoid biosynthesis
  作者：Benjamin R. Lichman、Mohamed O. Kamileen、Gabriel R. Titchiner、Gerhard Saalbach、Clare E. M. Stevenson、David M. Lawson、Sarah E. O’Connor

  DOI：10.1038/s41589-018-0185-2

  日期：2019.1

  NEPS1 provides nepetalactones, metabolites that are well known for both insect-repellent activity and euphoric effects in cats. Structural characterization of the NEPS3 cyclase reveals that it binds to NAD+ yet does not utilize it chemically for a non-oxidoreductive formal [4 + 2] cyclization. These discoveries will complement metabolic reconstructions of iridoid and monoterpene indole alkaloid biosynthesis

  萜烯合酶通常通过在单个酶活性位点中线性起始材料的协同活化和环化形成复杂的分子支架。在这里，我们显示环烯醚萜合酶，一种非典型的还原性萜烯合酶，催化其底物 8-氧代香叶醛活化为活性烯醇中间体，但不催化随后的环化为荆芥内醇。这一发现使我们从猫薄荷 ( Nepeta mussinii ) 中鉴定出一类与荆芥内醇相关的短链脱氢酶 (NEPS)) 捕获这种反应性中间体并催化立体选择性环化为不同的荆芥内酯立体异构体。NEPS1 对荆芥内酯的后续氧化提供荆芥内酯，这是众所周知的在猫中具有驱虫活性和欣快作用的代谢物。NEPS3 环化酶的结构表征表明它与 NAD +结合，但不会化学利用它进行非氧化还原形式的 [4 + 2] 环化。这些发现将补充环烯醚萜和单萜吲哚生物碱生物合成的代谢重建。