15,16-epoxyoctadeca-9,12-dienoic acid methyl ester

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 15,16-epoxyoctadeca-9,12-dienoic acid methyl ester
• 英文别名: methyl 15,16-epoxy-9,12-octadecadienoate；methyl ester of 15,16-epoxy-9,12-octadecadienoic acid；cis-15,16-epoxy octadec-9,12-dienoate methyl ester；15,16-Epoxy-9,12-octadecadiensaeure-methlester (cis,cis)；methyl (9Z,12Z)-14-(3-ethyloxiran-2-yl)tetradeca-9,12-dienoate
• 化学式: C₁₉H₃₂O₃
• 分子量: 308.461
• InChiKey: WXOURJJDULGFAF-DPTWWRMPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  22
• 可旋转键数：
  14
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  15,16-epoxyoctadeca-9,12-dienoic acid methyl ester 在 sodium acetate 、 溶剂黄146 作用下， 生成 15,16-DiHODE
  参考文献：
  名称：

  Kato, Tadahiro; Yamaguchi, Yoshihiro; Namai, Tsuneo, Bioscience, Biotechnology and Biochemistry, 1993, vol. 57, # 2, p. 283 - 287

  摘要：

  DOI：
• 作为产物：
  描述：

  Γ-十八碳三烯酸 在 盐酸 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 15,16-epoxyoctadeca-9,12-dienoic acid methyl ester
  参考文献：
  名称：

  Enantioselective epoxidation of linolenic acid catalysed by cytochrome P450BM3 from Bacillus megaterium

  摘要：

  来自大肠杆菌的细胞色素P450BM3催化亚油酸1的环氧化反应，生成15,16-环氧油酸2，具有完全的区域选择性和适度的对映选择性（60% ee）。产品的绝对构型暂时被指认为15(R),16(S)-。该反应的米哈利斯-门腾参数kcat和Km分别为3126 ± 226 min−1和24 ± 6 μM。

  DOI：

  10.1039/b506155e

文献信息

• Epoxidation, hydroxylation and aromatization is catalyzed by a peroxygenase from Solanum lycopersicum
  作者：Christopher Fuchs、Wilfried Schwab

  DOI：10.1016/j.molcatb.2013.07.001

  日期：2013.12

  bound recombinant SlPXG protein was used as enzyme source. Unsaturated fatty acids, fatty acid derivatives, and terpenes were epoxidized by SlPXG in the presence of various hydroperoxides exclusively at their cis-double bonds. Terpenes with p-menthene skeleton were transformed in different ways depending on their molecular structures. R-(+)- and S-(−)-limonene were converted to R-(+)-limonene-trans-1

  植物过氧合酶（PXG）通过将氢过氧化物的氧原子转移至双键来氧化不饱和脂肪酸，从而提供环氧化物。在这项工作中，我们研究了番茄中的PXG（茄属植物Solanum lycopersicum，SlPXG）催化多种天然产物氧化的潜力。甲SlPXG基因从番茄克隆，在酵母中异源表达与膜结合的重组SlPXG蛋白用作酶源。不饱和脂肪酸，脂肪酸衍生物和萜烯在各种氢过氧化物仅以其顺式-双键存在的情况下被SlPXG环氧化。萜烯与p-薄荷烯骨架根据其分子结构以不同方式转化。R-（+）-和S-（-）-柠檬烯转化为R-（+）-柠檬烯-反式-1,2-环氧化物（97％）和顺式-S-（-）-柠檬烯-1,2 -环氧化物（88％），而α-萜品烯被羟基化为顺式-1,4-二羟基-p-薄荷脑-2-烯，而γ-萜品烯被芳构化为对-cymene。在最后的反应中，氢过氧化物用作氢受体而不是氧供体。PXG似乎是一种通用的生物催化剂，能够执行各种
• Mild catalytic oxidations of unsaturated fatty acid methyl esters (FAMEs) by oxovanadium complexes
  作者：Martina Maya Cecchini、Francesco De Angelis、Claudio Iacobucci、Samantha Reale、Marcello Crucianelli

  DOI：10.1016/j.apcata.2016.01.045

  日期：2016.5

  A selection of unsaturated fatty acid methyl esters, namely methyl oleate (C18:1), methyl linoleate (C18:2) and methyl linolenate (C18:3) has been oxidized under mild homogeneous catalytic conditions, using a series of oxovanadium(IV) complexes containing 4-acyl-5-pyrazolone donor ligands with different substituents on acyl residue. The main goal was to evaluate the catalytic role exerted by oxovanadium(IV)

  使用一系列的氧钒（IV）在温和的均相催化条件下，氧化了一些不饱和脂肪酸甲酯，即油酸甲酯（C18：1），亚油酸甲酯（C18：2）和亚油酸甲酯（C18：3）。含4-酰基-5-吡唑啉酮供体配体的复合物，在酰基残基上具有不同的取代基。主要目标是评估作为前体配合物的氧钒金属（IV）在这些生物可再生资源的碳-碳双键的选择性氧官能化中发挥的催化作用，作为目前在工业中使用的更为剧烈的方法的绿色替代方案。工业水平。的三个基板，采用氧化叔以正丁基氢过氧化物为主要氧化剂，有或没有溶剂，在形成相应的单二和三环氧化物时，尤其是在无溶剂条件下，均显示出较高的起始原料转化率和较高的选择性。已通过ESI-MS对可能在简单FAME模型底物的叔丁基氢过氧化物氧化中起作用的催化循环机理进行了研究。
• Influence of alkenyl structures on the epoxidation of unsaturated fatty acid methyl esters and vegetable oils
  作者：Yao-Bing Huang、Meng-Yue Yao、Ping-Ping Xin、Meng-Chao Zhou、Tao Yang、Hui Pan

  DOI：10.1039/c5ra11035a

  日期：——

  Epoxidation of vegetable oils or fatty acid methyl esters (FAMEs) produce important monomers which are widely used as plasticizers or stabilizers in the polymer industry. However, little attention has been focused on the influence of the alkenyl structure of the fatty acid on the efficiency and selectivity of their epoxidation. In this work, the influence of the alkenyl structure (the number of double bonds)

  植物油或脂肪酸甲酯（FAME）的环氧化产生重要的单体，这些单体在聚合物工业中被广泛用作增塑剂或稳定剂。但是，很少有注意力集中在脂肪酸的烯基结构对其环氧化效率和选择性的影响上。在这项工作中，已研究了FAME的烯基结构（双键数）对环氧化反应的影响。使用弱酸（甲酸）和强酸（硫酸/乙酸）系统对具有1至3个双键的三个模型FAME进行环氧化。发现具有更多双键的FAME对环氧化反应具有更高的反应性。此外，脂肪酸链上双键的供电子作用趋于稳定与弱酸体系相邻的环氧化物。此外，具有更多双键的FAME容易与强酸体系发生副反应（H2 SO 4）。用相同的两种酸催化剂体系对具有不同脂肪酸组成的两种植物油进行环氧化。结果与FAME的结果一致。目前的发现可以为具有不同烯基结构组成的不同植物油的环氧化提供有用的指导。
• Epoxidation of Methyl Esters as Valuable Biomolecules: Monitoring of Reaction
  作者：Martin Hájek、Tomáš Hájek、David Kocián、Karel Frolich、András Peller

  DOI：10.3390/molecules28062819

  日期：——

  through a reaction and in the determination of time course. Through the epoxidation, many intermediates and final products were formed, i.e., epoxides with different number and/or different position of oxirane rings in carbon chain. For the determination, three main methods (infrared spectroscopy, high-pressure liquid chromatography and gas chromatography with mass spectrometry) were applied. Only gas chromatography

  本文重点研究了从油料作物制备的甲酯的环氧化反应，这些油料作物具有各种高级脂肪酸，尤其是不饱和脂肪酸，主要包含在非食用亚麻籽和亚麻荠油（第二代）中。新颖性在于分离和鉴定所有具有通过反应形成的环氧乙烷环的产物和时程的测定。通过环氧化，形成许多中间体和最终产物，即在碳链中具有不同数目和/或不同位置的环氧乙烷环的环氧化物。对于测定，应用了三种主要方法（红外光谱法、高压液相色谱法和气相色谱法与质谱法）。只有气相色谱法能够分离单个环氧化物，根据产物的质谱、分子离子和时程进行鉴定。中间体的测定可以：(i) 控制环氧化过程，(ii) 详细测定环氧化物的混合物，从而计算每种产品的选择性。因此，环氧化反应将更加环保，特别是对于含有大量不饱和脂肪酸的非食用油料作物的高级应用。
• A non-canonical caleosin from<i>Arabidopsis</i>efficiently epoxidizes physiological unsaturated fatty acids with complete stereoselectivity
  作者：Elizabeth Blée、Martine Flenet、Benoît Boachon、Marie-Laure Fauconnier

  DOI：10.1111/j.1742-4658.2012.08757.x

  日期：2012.10

  In plants, epoxygenated fatty acids (EFAs) are constituents of oil seeds as well as defence molecules and components of biopolymers (cutin, suberin). While the pleiotropic biological activities of mammalian EFAs have been well documented, there is a paucity of information on the physiological relevance of plant EFAs and their biosynthesis. Potential candidates for EFA formation are caleosin‐type peroxygenases which catalyze the epoxidation of unsaturated fatty acids in the presence of hydroperoxides as co‐oxidants. However, the caleosins characterized so far, which are mostly localized in seeds, are poor epoxidases. In sharp contrast, quantitative RT‐PCR analysis revealed that PXG4, a class II caleosin gene, is expressed in roots, stems, leaves and flowers of Arabidopsis. Expressed in yeast, PXG4 encodes a calcium‐dependent membrane‐associated hemoprotein able to catalyze typical peroxygenase reactions. Moreover, we show here that purified recombinant PXG4 is an efficient fatty acid epoxygenase, catalyzing the oxidation of cis double bonds of unsaturated fatty acids. Physiological linoleic and linolenic acids proved to be the preferred substrates for PXG4; they are oxidized into the different positional isomers of the monoepoxides and into diepoxides. An important regioselectivity was observed; the C‐12,13 double bond of these unsaturated fatty acids being the least favored unsaturation epoxidized by PXG4, linolenic acid preferentially yielded the 9,10‐15,16‐diepoxide. Remarkably, PXG4 catalyzes exclusively the formation of (R),(S)‐epoxide enantiomers, which is the absolute stereochemistry of the epoxides found in planta. These findings pave the way for the study of the functional role of EFAs and caleosins in plants.