(E,E)-2,6-二甲基-2,6-辛二烯二醛 | 80054-40-6

• 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
• 中文名称: (E,E)-2,6-二甲基-2,6-辛二烯二醛
• 英文名称: 10-oxogeranial
• 英文别名: (2E,6E)-2,6-dimethylocta-2,6-dienedial
• CAS: 80054-40-6
• 化学式: C₁₀H₁₄O₂
• 分子量: 166.22
• InChiKey: GRHWFPUCRVCMRY-TXFIJWAUSA-N

物化性质

• 沸点：
  307.7±30.0 °C(Predicted)
• 密度：
  0.949±0.06 g/cm3(Predicted)
• 溶解度：
  可溶于氯仿（少许）、乙酸乙酯（少许）、甲醇（少许）

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E,E)-2,6-二甲基-2,6-辛二烯二醛 在 还原型辅酶II(NADPH)四钠盐 作用下， 生成 iridodial
  参考文献：
  名称：

  虹膜形成机制的阐明-从细胞悬浮培养物中部分纯化和鉴定新型单萜环化酶

  摘要：

  从10-羟基香叶醇和细胞悬浮培养物的粗酶提取物的培养系统中，分离出10-氧香叶醇，10-羟基香叶醛和10-氧香叶醛。对于这三种化合物，已证明在铱的生物合成中具有先驱作用。这一事实明确地证实了我们先前对虹膜二代生物合成的主张。另外，部分纯化并表征了催化虹彩形成的新型单萜环化酶。

  DOI：

  10.1016/s0040-4039(00)96530-4
• 作为产物：
  描述：

  (E)-3,7-二甲基-2,6-辛二烯醛 在 selenium(IV) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 72.0h， 以19%的产率得到(E,E)-2,6-二甲基-2,6-辛二烯二醛
  参考文献：
  名称：

  结合 NAD+、NADPH 或 NAD+/10-Oxogeranial 的长春花环烯醚萜合成酶的结构：反应机制

  摘要：

  解析了在 NAD +、NADPH 或 NAD + /10-oxogeranial存在下环烯醚萜合酶荆芥内酯合酶的结构。10-氧香茅醛底物以反式-O1-C3构象结合，并且可以通过氢化物加成还原，形成副产物S -10-氧代-香茅醛。Tyr178 O z 位于距底物 O1 2.5 Å 的位置，提供反应所需的第二个质子。荆芥内酯产物的形成需要围绕 C1-C2 旋转形成顺式异构体，从而形成顺式烯醇化物，同时围绕 C4-C5 旋转，从而实现环化和乳醇生产。其结构与孕酮-5β-还原酶相似，NADP、Lys146(147)、Tyr178(179) 和 F342(343) 的定位几乎相同，但只有 Tyr178 和 Phe342 似乎对活性至关重要。反式10-氧香叶醛结构也可作为黄体酮5β-还原酶中β-面氢化物攻击的模型，并且在不对称合成中受到普遍关注。

  DOI：

  10.1002/anie.201508310

文献信息

• 1,4-Bis-Dipp/Mes-1,2,4-Triazolylidenes: Carbene Catalysts That Efficiently Overcome Steric Hindrance in the Redox Esterification of α- and β-Substituted α,β-Enals
  作者：Veera Reddy Yatham、Wacharee Harnying、Darius Kootz、Jörg-M. Neudörfl、Nils E. Schlörer、Albrecht Berkessel

  DOI：10.1021/jacs.5b11796

  日期：2016.3.2

  2,4-triazolium salts were synthesized and evaluated as (pre)catalysts in the redox esterification of various α- or β-substituted enals. In particular the 1,4-bis-Mes/Dipp-1,2,4-triazolylidenes overcome the above limitations and efficiently catalyze the redox esterification of a whole series of α/β-substituted enals hitherto not amenable to NHC-catalyzed transformations. The synthetic value of 1,4-bis-Mes/Dipp-1

  正如 Scheidt 和 Bode 在 2005 年报道的那样，在醇和 N-杂环卡宾催化剂（例如苯并咪唑亚基或三唑基亚基）的存在下，空间无阻碍的 α,β-烯醛很容易转化为饱和酯。然而，α,β-烯醛底物的α-或β-位上的取代基通常是不能容忍的，因此严重限制了底物光谱。在我们早期的机理研究的基础上，合成了一组 N-Mes- 或 N-Dipp-取代的 1,2,4-三唑鎓盐，并在各种 α- 或 β- 的氧化还原酯化反应中作为（预）催化剂进行了评估。取代的埃纳尔。特别是 1,4-bis-Mes/Dipp-1,2,4-triazolylidenes 克服了上述限制，并有效地催化了一系列 α/β-取代烯醛的氧化还原酯化反应，迄今为止无法进行 NHC 催化转化。
• Resolution of an Iridoid Synthon, Gastrolactol, by Means of Dynamic Acetylation and Lipase-Catalyzed Alcoholysis
  作者：Ellen M. Santangelo、Didier Rotticci、Ilme Liblikas、Torbjörn Norin、C. Rikard Unelius

  DOI：10.1021/jo015592y

  日期：2001.8.1

  A short synthetic route to asymmetric iridoids was developed. The three key steps were an intramolecular [4 + 2] cycloaddition reaction of an enamine derivative of 8-oxocitral (2), a dynamic acetylation, and an enzymatic resolution of the gastrolactyl acetates 5a and 5b, iridoids with three stereocenters. Some regio- and stereoselective heterogeneous catalytic hydrogenations of double bonds in iridoid

  开发了合成不对称虹彩的简短途径。这三个关键步骤是8-氧肟酸酯（2）的烯胺衍生物的分子内[4 + 2]环加成反应，动态乙酰化以及乙酸甘油酯乙酸酯5a和5b的酶解，具有三个立体中心的虹彩化合物。讨论了环烯基配体中双键的一些区域和立体选择性非均相催化加氢反应。
• Biosynthesis of Defensive Allomones in Leaf Beetle Larvae: Stereochemistry of Salicylalcohol Oxidation in Phratora vitellinae and Comparison of Enzyme Substrate and Stereospecificity with Alcohol Oxidases from Several Iridoid Producing Leaf Beetles
  作者：Martin Veith、Neil J. Oldham、Konrad Dettner、Jacques M. Pasteels、Wilhelm Boland

  DOI：10.1023/b:joec.0000006369.26490.c6

  日期：1997.2

  (7S)-[H-2(5)]-Salicylalcohol (3) and (7R)-[H-2(1)]-salicylalcohol (5) have been synthesized in order to examine the stereospecificity of salicylalcohol oxidase from the defensive secretion of the salicylaldehyde-producing leaf beetle Phratora vitellinae. Oxidation was found to proceed by selective removal of the C(7)-H-R hydrogen atom (Re-specificity) to yield salicylaldehyde. (7S)-[H-2(6)]-Benzylalcohol (9) was also oxidized Re-specifically to benzaldehyde, but in much lower yield, indicating the importance of the orthohydroxy group of salicylalcohol in substrate enzyme binding. The stereospecificities of terpenoid oxidases from six species of iridoid-producing leaf beetle were examined using (1R,8R)-[H-2(2)]-8-hydroxygeraniol (10), and were all found to oxidize the substrate Re-specifically. Cross-activity of oxidation was found in a number of species, with P. vitellinae able to oxidize terpenoid (10) and two of the iridoid-producing species able to oxidize salicylalcohol analogue (3), again with Re-specificity. However, when the two substrate analogs were presented together, in equal concentrations, preferential oxidation of the natural analog was observed in each case. The kinetics of oxidation for a number of terpenoid and aromatic alcohols by the defensive secretion of the iridoid-producing leaf beetle Phaedon armoraciae have been studied, revealing a large difference between the rate of(primary, allylic) terpenoid alcohol oxidation and the rate of salicylalcohol oxidation, thus accounting for the observed selectivity.

  为了研究来自分泌水杨醛的叶甲Phratora vitellinae防御分泌物的水杨醛醇氧化酶的立体特异性，合成了(7S)-[H-2(5)]-水杨醛醇(3)和(7R)-[H-2(1)]-水杨醛醇(5)。发现氧化反应通过选择性地去除C(7)-H-R氢原子（Re特异性）来生成水杨醛。另外，(7S)-[H-2(6)]-苯甲醇(9)也被Re特异性地氧化为苯甲醛，但产率较低，这表明水杨醛醇中的邻羟基在底物与酶的结合中非常重要。 使用(1R,8R)-[H-2(2)]-8-羟基香叶醇(10)，研究了来自六种产生吲哚苷的叶甲的萜类氧化酶的立体特异性，发现所有酶都对底物进行Re特异性的氧化。在多个物种中发现了氧化反应的交叉活性，Phratora vitellinae能够氧化萜类(10)，而两种产生吲哚苷的物种能够氧化水杨醛醇类似物(3)，同样具有Re特异性。然而，当两种底物类似物以相等浓度同时存在时，每种情况下都观察到对天然底物类似物的选择性氧化。 还研究了由产生吲哚苷的叶甲Phaedon armoraciae防御分泌物对多种萜类和芳族醇的氧化动力学，揭示了(主要，烯丙位)萜类醇氧化速率与水杨醛醇氧化速率之间存在显著差异，从而解释了观察到的选择性。
• 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。