15R,16S-epoxy-octadeca-9Z,12Z-dienoic acid | 403656-25-7

• 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: 15R,16S-epoxy-octadeca-9Z,12Z-dienoic acid
• 英文别名: (15R,16S)-epoxyoctadeca-9,12-dienoic acid；(15R,16S)-epoxy-α-linolenic acid；15,16-Epoxylinoleic acid；(9Z,12Z)-14-[(2R,3S)-3-ethyloxiran-2-yl]tetradeca-9,12-dienoic acid
• CAS: 403656-25-7
• 化学式: C₁₈H₃₀O₃
• 分子量: 294.434
• InChiKey: HKSDVVJONLXYKL-YNOGVTSOSA-N

物化性质

• 沸点：
  399.4±17.0 °C(Predicted)
• 密度：
  0.983±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  21
• 可旋转键数：
  13
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  49.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  15R,16S-epoxy-octadeca-9Z,12Z-dienoic acid 在 arachidonate 8-lipoxygenase 、 tin(ll) chloride 作用下， 以 aq. phosphate buffer 为溶剂， 生成
  参考文献：
  名称：

  脂氧合酶催化环氧脂肪酸转化为羟基内过氧化物：潜在的 P450 和脂氧合酶相互作用。

  摘要：

  在此，我们描述了脂氧合酶 (LOX) 对脂肪酸环氧化物的普遍适用转化，该转化导致最终产品中形成五元内过氧化物环。我们在 15,16-环氧-α-亚麻酸代谢中使用大豆 LOX-1 以及在 14,15-环氧二十碳三烯酸代谢中使用鼠血小板型 12-LOX 和人 15-LOX-1 证明了这种转化。 14,15-EET）。对大豆 LOX-1 对 15,16-环氧-α-亚麻酸的两种对映异构体的转化进行的详细检查表明，预期的主要产物 13S-氢过氧-15,16-环氧化物在缓冲液中经历了非酶促转化转化为一种新的衍生物，经 HPLC 纯化，经 UV、LC-MS 和 1H-NMR 鉴定为 13,15-endoperoxy-16-hydroxy-octadeca-9,11-dienoic acid。内过氧化物的构型（顺式或反式侧链）取决于新的氢过氧部分与脂肪酸环氧化物的对映体构型的空间关系。反应机理涉及氢过氧（亲

  DOI：

  10.1194/jlr.m054072
• 作为产物：
  描述：

  (9Z,12Z)-(15S,16S)-15-Bromo-16-((R)-3,3,3-trifluoro-2-methoxy-2-phenyl-propionyloxy)-octadeca-9,12-dienoic acid methyl ester 在 lithium hydroxide 作用下， 以 1,4-二氧六环 为溶剂， 反应 36.0h， 生成 15R,16S-epoxy-octadeca-9Z,12Z-dienoic acid
  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

• Enantioselective epoxidation of linolenic acid catalysed by cytochrome P450BM3 from Bacillus megaterium
  作者：Ayhan Çelik、Davide Sperandio、Robert E. Speight、Nicholas J. Turner

  DOI：10.1039/b506155e

  日期：——

  Cytochrome P450BM3, from Bacillus megaterium, catalyses the epoxidation of linolenic acid 1 yielding 15,16-epoxyoctadeca-9,12-dienoic acid 2 with complete regio- and moderate enantio-selectivity (60% ee). The absolute configuration of the product is tentatively assigned as 15(R),16(S)-. The Michaelis–Menten parameters kcat and Km for the reaction were determined to be 3126 ± 226 min−1 and 24 ± 6 μM respectively.

  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。
• Preparation of the enantiomers of hydroxy-C18 fatty acids and their anti-rice blast fungus activities
  作者：Tadahiro Kato、Toshio Nakai、Rumiko Ishikawa、Aya Karasawa、Tsuneo Namai

  DOI：10.1016/s0957-4166(01)00486-4

  日期：2001.10

  the infected rice plants as an enantiomeric mixture with <10% e.e., a procedure for the chemical preparation of both enantiomers was explored, starting from the original fatty acids 4 and 5. The anti-rice blast fungus activities of both enantiomers of the allylic alcohols 1–3 and epoxy α-linolenic acids 12 and 13 demonstrate no noticeable correlation between the activity and chirality.

  为了检查抗稻瘟病菌的活性和烯丙基醇的手性之间的相关性1 - 3，这是从受感染的水稻植物，其特征为具有<10％ee的，对于两者的化学制备过程对映体混合物从原始脂肪酸4和5开始探索对映体。烯丙基醇的两种对映体的抗稻瘟病菌的活动13和环氧树脂α-亚麻酸12和13表现出的活性和手性之间没有明显的相关性。
• Lipoxygenase-catalyzed transformation of epoxy fatty acids to hydroxy-endoperoxides: a potential P450 and lipoxygenase interaction
  作者：Tarvi Teder、William E. Boeglin、Alan R. Brash

  DOI：10.1194/jlr.m054072

  日期：2014.12

  examination of the transformation of the two enantiomers of 15,16-epoxy-α-linolenic acid by soybean LOX-1 revealed that the expected primary product, a 13S-hydroperoxy-15,16-epoxide, underwent a nonenzymatic transformation in buffer into a new derivative that was purified by HPLC and identified by UV, LC-MS, and ¹H-NMR as a 13,15-endoperoxy-16-hydroxy-octadeca-9,11-dienoic acid. The configuration of the endoperoxide

  在此，我们描述了脂氧合酶 (LOX) 对脂肪酸环氧化物的普遍适用转化，该转化导致最终产品中形成五元内过氧化物环。我们在 15,16-环氧-α-亚麻酸代谢中使用大豆 LOX-1 以及在 14,15-环氧二十碳三烯酸代谢中使用鼠血小板型 12-LOX 和人 15-LOX-1 证明了这种转化。 14,15-EET）。对大豆 LOX-1 对 15,16-环氧-α-亚麻酸的两种对映异构体的转化进行的详细检查表明，预期的主要产物 13S-氢过氧-15,16-环氧化物在缓冲液中经历了非酶促转化转化为一种新的衍生物，经 HPLC 纯化，经 UV、LC-MS 和 1H-NMR 鉴定为 13,15-endoperoxy-16-hydroxy-octadeca-9,11-dienoic acid。内过氧化物的构型（顺式或反式侧链）取决于新的氢过氧部分与脂肪酸环氧化物的对映体构型的空间关系。反应机理涉及氢过氧（亲
• 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.