5(S)-HETE methyl ester | 78037-99-7

• 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: 5(S)-HETE methyl ester
• 英文别名: 5-Hete methyl ester；methyl (5S,6E,8Z,11Z,14Z)-5-hydroxyicosa-6,8,11,14-tetraenoate
• CAS: 78037-99-7
• 化学式: C₂₁H₃₄O₃
• 分子量: 334.499
• InChiKey: RWLSHOXCJVZJMD-KPMWKZHNSA-N

物化性质

• 沸点：
  447.7±45.0 °C(Predicted)
• 密度：
  0.952±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  24
• 可旋转键数：
  15
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5(S)-HETE methyl ester 在 lithium hydroxide 作用下， 以 四氢呋喃 、 水 为溶剂， 以90%的产率得到5(S)-羟化二十烷四烯酸
  参考文献：
  名称：

  A General Strategy for the Synthesis of Monohydroxy-eicosatetraenoic Acids: Total Synthesis of 5(S)-Hydroxy-6(E),8,11,14(Z)-eicosatetraenoic Acid (5-HETE) and 12(S)-Hydroxy-5,8,14(Z), 10(E)-eicosatetraenoic Acid (12-HETE)

  摘要：

  通过钯(0)-铜(I)耦合技术合成5(S)-羟基-6(E),8, 11,14(Z)-二十碳四烯酸（5-HETE）和12(S)-羟基-5,8,14(Z), 10(E)-二十碳四烯酸（12-HETE）的立体选择性全合成过程被描述。

  DOI：

  10.1055/s-1986-31612
• 作为产物：
  描述：

  花生四烯酸 在 potato lipoxygenase sodium tetrahydroborate 、 氧气 、 potassium carbonate 作用下， 以 乙醚 、 乙醇 为溶剂， 反应 0.24h， 生成 5(S)-HETE methyl ester
  参考文献：
  名称：

  Stereochemistry and mechanism of the biosynthesis of leukotriene A4 from 5(S)-hydroperoxy-6(E),8,11,14(Z)-eicosatetraenoic acid. Evidence for an organoiron intermediate

  摘要：

  DOI：

  10.1021/ja00186a046

文献信息

• An efficient total synthesis of 5-(S)-HETE
  作者：Sylvie Gueugnot、Mouâd Alami、Gérard Linstrumelle、Lengo Mambu、Yves Petit、Marc Larchevêque

  DOI：10.1016/0040-4020(96)00316-x

  日期：1996.5

  A short and convergent synthesis of (5S)-HETE 1a was accomplished by coupling of two easily accessible synthons 2 and 3a.

  短而收敛的合成（5 S）-HETE 1a是通过耦合两个易于访问的合成子2和3a来完成的。
• A practical process for large-scale synthesis of (S)-5-hydroxy-6-trans-8,11,14-cis-eicosatetraenoic acid (5-HETE)
  作者：E.J. Corey、Shun-ichi Hashimoto

  DOI：10.1016/0040-4039(81)80080-9

  日期：1981.1

  ()-5-Hydroxy-6--8,11,14--eicosatetraenoic acid (5-HETE) (1) and its enantiomer are readily available by a chemical synthesis from arachidonic acid which includes a chromatographic separation of diastereomeric urethanes (3) made from (±)-5-HETE methyl ester and the isocyanate 4 derived from dehydroabietylamine.

  （）-5-羟基-6- -8,11,14-二十碳四烯酸（5-HETE）（1）及其对映异构体可通过花生四烯酸的化学合成方法容易地获得，其中包括色谱分离非对映氨基甲酸乙酯（3 ）由（±）-5-HETE甲酯和脱氢松香胺衍生的异氰酸酯4制成。
• Reductive deprotection of silyl groups with Wilkinson’s catalyst/catechol borane
  作者：Pranav Patel、Chih-Tsung Chang、Namin Kang、Gue-Jae Lee、William S. Powell、Joshua Rokach

  DOI：10.1016/j.tetlet.2007.05.118

  日期：2007.7

  Traditionally silyl groups are deprotected with acids and fluorides. These methods are, however, less discriminating when multi-silyl groups are present in the same molecule resulting in lower yields of desired products. The manipulation of these functions during the total synthesis of natural products, e.g. prostaglandins and isoprostanes, requires the selective protection and deprotection of these

  传统上，甲硅烷基是用酸和氟化物脱保护的。然而，当同一分子中存在多甲硅烷基时，这些方法的区别较小，导致所需产物的产率较低。在天然产物（例如前列腺素和异前列腺素）的全合成过程中对这些功能的操纵需要对这些基团进行选择性保护和脱保护。 /邻苯二酚硼烷或单独的邻苯二酚硼烷。
• Biosynthetic Crossover of 5-Lipoxygenase and Cyclooxygenase-2 Yields 5-Hydroxy-PGE₂ and 5-Hydroxy-PGD₂
  作者：Fumie Nakashima、Takashi Suzuki、Odaine N. Gordon、Dominic Golding、Toshiaki Okuno、Juan A. Giménez-Bastida、Takehiko Yokomizo、Claus Schneider

  DOI：10.1021/jacsau.1c00177

  日期：2021.9.27

  (COX-2) enzymatic activities is a productive pathway to convert arachidonic acid into unique eicosanoids. Here, we show that COX-2 catalysis with 5-LOX derived 5-hydroxy-eicosatetraenoic acid yields the endoperoxide 5-hydroxy-PGH2 that spontaneously rearranges to 5-OH-PGE2 and 5-OH-PGD2, the 5-hydroxy analogs of arachidonic acid derived PGE2 and PGD2. The endoperoxide was identified via its predicted

  5-脂氧合酶 (5-LOX) 和环氧合酶-2 (COX-2) 酶活性的生物合成交叉是将花生四烯酸转化为独特的类二十烷酸的有效途径。在这里，我们表明 COX-2 催化 5-LOX 衍生的 5-羟基-二十碳四烯酸产生内过氧化物 5-羟基-PGH 2 ，它自发重排为 5-OH-PGE 2和 5-OH-PGD 2 ，即 5-OH-PGD 2 。花生四烯酸衍生的PGE 2和PGD 2的羟基类似物。内过氧化物通过其预测的降解产物5,12-二羟基-十七-6 E ,8 E ,10 E -烯酸以及SnCl 2介导的5-OH-PGF 2α还原来鉴定。 5-OH-PGE 2和5-OH-PGD 2均不稳定并且在弱碱处理后迅速降解。这种不稳定性阻碍了生物样品中的检测，通过使用 NaBH 4原位还原产生相应的稳定 5-OH-PGF 2非对映异构体克服了这种不稳定性，并能够在活化的原代人白细胞中检测 5-OH-PGF 2α
• Identification and absolute configuration of dihydroxy-arachidonic acids formed by oxygenation of 5S-HETE by native and aspirin-acetylated COX-2
  作者：Surafel Mulugeta、Takashi Suzuki、Noemi Tejera Hernandez、Markus Griesser、William E. Boeglin、Claus Schneider

  DOI：10.1194/jlr.m001719

  日期：2010.3

  Biosynthesis of the prostaglandin endoperoxide by the cyclooxygenase (COX) enzymes is accompanied by formation of a small amount of 11R-hydroxyeicosatetraenoic acid (HETE), 15R-HETE, and 15S-HETE as by-products. Acetylation of COX-2 by aspirin abrogates prostaglandin synthesis and triggers formation of 15R-HETE as the sole product of oxygenation of arachidonic acid. Here, we investigated the formation of by-products of the transformation of 5S-HETE by native COX-2 and by aspirin-acetylated COX-2 using HPLC-ultraviolet, GC-MS, and LC-MS analysis. 5S,15S- dihydroxy (di)HETE, 5S,15R-diHETE, and 5S,11R-diHETE were identified as by-products of native COX-2, in addition to the previously described di-endoperoxide (5S,15S-dihydroxy-9S,11R,8S,12S-diperoxy-6E,13E-eicosadienoic acid) as the major oxygenation product. 5S,15R-diHETE was the only product formed by aspirin-acetylated COX-2. Both 5,15-diHETE and 5,11-diHETE were detected in CT26 mouse colon carcinoma cells as well as in lipopolysaccharide-activated RAW264.7 cells incubated with 5S-HETE, and their formation was attenuated in the presence of the COX-2 specific inhibitor, NS-398. Aspirin-treated CT26 cells gave 5,15-diHETE as the most prominent product formed from 5S-HETE. 5S,15S-diHETE has been described as a product of the cross-over of 5-lipoxygenase (5-LOX) and 15-LOX activities in elicited rat mononuclear cells and human leukocytes, and our studies implicate crossover of the 5-LOX and COX-2 pathways as an additional bio-synthetic route.-Mulugeta, S., T. Suzuki, N. T. Hernandez, M. Griesser, W. E. Boeglin, and C. Schneider. Identification and absolute configuration of dihydroxy-arachidonic acids formed by oxygenation of 5S-HETE by native and aspirin-acetylated COX-2. J. Lipid Res. 2010. 51: 575-585.