(15S,16R)-epoxy-α-linolenic 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: (15S,16R)-epoxy-α-linolenic acid methyl ester
• 英文别名: methyl cis-15,16-epoxy-9Z,12Z-octadecadienoate；methyl (9Z,12Z)-14-[(2S,3R)-3-ethyloxiran-2-yl]tetradeca-9,12-dienoate
• 化学式: C₁₉H₃₂O₃
• 分子量: 308.461
• InChiKey: WXOURJJDULGFAF-HULPXVQOSA-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

• 作为产物：
  描述：

  15-bromo-16-hydroxy-α-linolenic acid methyl ester 在 1,4,8,11-四硫杂环十四烷 、 lithium hydroxide 、 Lipase PS 、 4 A molecular sieve 作用下， 以 1,4-二氧六环 、 乙醚 、 正己烷 为溶剂， 反应 40.0h， 生成 (15S,16R)-epoxy-α-linolenic acid methyl ester
  参考文献：
  名称：

  Preparation of Optically Active 15-Epoxy-a-linolenic Acids and Their Anti-Rice Blast Fungus Activities

  摘要：

  By the action of NBS in aq. DME, alpha-linolenic acid was oxidized to 15-bromo-16-hydroxy-alpha-linolenic acid in 35% conversion yield. The bromohydrin was treated with lipase-PS and vinyl acetate to give the resolved acetate and bromohydrin. (15S,16R)- and (15R,16S)-Epoxy-alpha-linolenic acids were prepared from the corresponding resolved products. A comparison of anti-rice blast fungus activities showed that an unnatural epoxide is stronger than the natural epoxide.

  DOI：

  10.3987/com-99-s147

文献信息

• Selective Oxidation Reactions of Natural Compounds with Hydrogen Peroxide Mediated by Methyltrioxorhenium
  作者：Maria Amato、Francesco Ballistreri、Andrea Pappalardo、Gaetano Tomaselli、Rosa Toscano、Giuseppe Sfrazzetto

  DOI：10.3390/molecules181113754

  日期：——

  We have investigated the oxidative behaviour of natural compounds such as methyl abietate (1), farnesyl acetate (2), α-ionone (3), β-ionone (4), methyl linolelaidate (5), methyl linolenate (6) and bergamottin (7) with the oxidant system methyltrioxo-rhenium/ H2O2/pyridine. The reactions, performed in CH2Cl2/H2O at 25 °C, have shown good regio- and stereoselectivity. The oxidation products were isolated by HPLC or silica gel chromatography and characterized by MS(EI), 1H-, 13C-NMR, APT, gCOSY, HSQC, TOCSY and NOESY measurements. The selectivity seems to be controlled by the nucleophilicity of double bonds and by stereoelectronic and steric effects.

  我们已经研究了天然化合物如松香酸甲酯（1）、金合欢基乙酸酯（2）、α-紫罗酮（3）、β-紫罗酮（4）、亚油酸甲酯（5）、亚麻酸甲酯（6）和佛手柑素（7）在与氧化剂系统甲基三氧化铼/过氧化氢/吡啶中的氧化行为。这些反应在25°C下进行于CH2Cl2/H2O中，并显示出良好的区域选择性和立体选择性。氧化产物通过高效液相色谱或硅胶柱色谱分离，并通过质谱（EI）、1H-、13C-核磁共振、APT、gCOSY、HSQC、TOCSY和NOESY测量进行表征。选择性似乎受到双键亲核性以及立体电子和空间效应的控制。
• Monoepoxy octadecadienoates and monoepoxy octadecatrienoates
  作者：Pei H. Cui、Rujee K. Duke、Colin C. Duke

  DOI：10.1016/j.chemphyslip.2008.02.003

  日期：2008.4

  correlated spectroscopy (COSY) and 1H-13C heteronuclear correlation (HETCOR). The proton and carbon NMR chemical shifts of the epoxide, the double bonds, and the interrupted methylenes are assigned. Also discussed is an interpretation of the 1H and 13C NMR spectra of these monoepoxides including the changes in the 13C resonance of the olefinic carbons on the neighboring double bonds resulting from epoxide

  使用间氯过苯甲酸将γ-亚麻酸，α-亚麻酸和十八碳四烯酸的甲酯环氧化，得到九种顺式-单环氧-C18脂肪酸甲酯（FAME），包括新型的十八烷基-甲基-顺式-单环氧衍生物和γ-亚麻酸的顺式-6,7-环氧衍生物。这九种单环氧FAME通过正相HPLC纯化，通过LC-MS，1H和13C NMR鉴定，并通过质谱和NMR光谱进行表征。这项研究的重点是使用NMR光谱技术，包括1H，13C，1H-1H相关光谱（COSY）和1H-13C异核相关（HETCOR），对这些C18单环氧FAME进行结构表征。确定了环氧化物，双键和间断亚甲基的质子和碳NMR化学位移。
• Preparation of Optically Active 15-Epoxy-a-linolenic Acids and Their Anti-Rice Blast Fungus Activities
  作者：Tadahiro Kato、Toshio Nakai、Takayuki Ishimatu、Masahiro Hoshikawa、Tsuneo Namai

  DOI：10.3987/com-99-s147

  日期：——

  By the action of NBS in aq. DME, alpha-linolenic acid was oxidized to 15-bromo-16-hydroxy-alpha-linolenic acid in 35% conversion yield. The bromohydrin was treated with lipase-PS and vinyl acetate to give the resolved acetate and bromohydrin. (15S,16R)- and (15R,16S)-Epoxy-alpha-linolenic acids were prepared from the corresponding resolved products. A comparison of anti-rice blast fungus activities showed that an unnatural epoxide is stronger than the natural epoxide.