(9Z,11E,13S)-13-hydroxyoctadeca-9,11-dienoic acid methyl ester | 24058-13-7

• 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: (9Z,11E,13S)-13-hydroxyoctadeca-9,11-dienoic acid methyl ester
• 英文别名: (13S)-hydroxylinoleic acid methyl ester；13S-hydroxy-9Z,11E-octadecadienoic acid methyl ester；methyl 13(S)-hydroxy-9(Z),11(E)-octadecadienoate；(+)-Methyl coriolate；(13S,9Z,11E)-13-hydroxyoctadeca-9,11-dienoic acid methyl ester；methyl (S,9Z,11E)-13-hydroxyoctadeca-9,11-dienoate；(S)-coriolic acid methyl ester；MHOD；13(S)-HODE methyl ester；methyl (9Z,11E,13S)-13-hydroxyoctadeca-9,11-dienoate
• CAS: 24058-13-7
• 化学式: C₁₉H₃₄O₃
• 分子量: 310.477
• InChiKey: ZVMLLPSSQZSZOA-QGWXGPBYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  22
• 可旋转键数：
  15
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.74
• 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：

  (9Z,11E,13S)-13-hydroxyoctadeca-9,11-dienoic acid methyl ester 在 sodium tetrahydroborate 、 cerium(III) chloride 、 戴斯-马丁氧化剂 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 7.16h， 生成 methyl coriolate
  参考文献：
  名称：

  Easy access to various natural keto polyunsaturated fatty acids and their corresponding racemic alcohols

  摘要：

  Various optically active hydroxy derivatives of polyunsaturated fatty acids were easily oxidised to their corresponding keto derivatives using Dess-Martin periodinane. The reaction was run on the millimolar scale with good yields and without appreciable isomerisation of the surrounding double bonds. Reduction of these keto compounds to yield back the starting alcohols, but now as racemic mixtures, was also conducted using CeCl3-NaBH4, once again without noticeable modification of the stereochemistry of the double bonds. These reactions proved the usefulness of the chemoenzymatic access to oxylipins through the use of lipoxygenases with various regiospecificity, combined with chemical transformations of the formed hydro(pero)xides. (C) 2003 Elsevier Ireland Ltd. All rights reserved.

  DOI：

  10.1016/s0009-3084(03)00087-2
• 作为产物：
  描述：

  (S)-tert-butyldimethyl(oct-1-yn-3-yloxy)silane 在 甲醇 、 copper(l) iodide 、 四(三苯基膦)钯 、 二氯二茂锆 、 四丁基氟化铵 、 copper diacetate 、 silver nitrate 、 lithium tri-t-butoxyaluminum hydride 、 二乙胺 、 锌 作用下， 以 四氢呋喃 、 水 、 苯 为溶剂， 反应 39.17h， 生成 (9Z,11E,13S)-13-hydroxyoctadeca-9,11-dienoic acid methyl ester
  参考文献：
  名称：

  13-羟基十八碳二烯酸二十二碳六烯酸酯的两种对映体的合成（13-DHAHLA）

  摘要：

  最近，已经报道了几种不同类别的内源脂质，它们显示出抗糖尿病和抗炎作用。由于它们在人体样品中的存在极少，因此对于精确的结构阐明和广泛的生物学评估，必须获得每种对映异构体的合成材料。在本文中，我们报道了从市售的起始原料的十三-羟基十八碳二烯酸二十二碳六烯酸酯（13-DHAHLA）的两种对映异构体的多毫克合成。

  DOI：

  10.1016/j.tetlet.2019.151331

文献信息

• A novel chemo-enzymatic enantiospecific synthesis of (S)-coriolic acid mediated via immobilized alcohol dehydrogenase of baker's yeast
  作者：U.T. Bhalerao、L. Dasaradhi、C. Muralikrishna、N.W. Fadnavis

  DOI：10.1016/s0040-4039(00)77613-1

  日期：1993.4

  (S)-(E)-(+)-1-Bromo-1-octene-3-ol was prepared in 85% yield and high optical purity (e.e. 97.4%) via a stereospecific reduction of corresponding bromo vinyl ketone using alcohol dehydrogenase from baker's yeast (EC 1.1.1.1) and NAD(P)H immobilized on Nucleosil 120-5 C18, and converted to 13(S)-hydroxy-9Z,11E-octadecadienoic (coriolic) acid.

  （S）-（E）-（+）-1-溴-1-辛烯-3-醇以85％的收率和高光学纯度（ee 97.4％）制备，方法是使用醇脱氢酶将相应的溴乙烯基酮立体定向还原。面包酵母（EC 1.1.1.1）和NAD（P）H固定在Nucleosil 120-5 C 18上，并转化为13（S）-羟基-9Z，11E-十八碳二烯酸（coriolic）酸。
• Direct synthesis of Z-alkenyl halides through catalytic cross-metathesis
  作者：Ming Joo Koh、Thach T. Nguyen、Hanmo Zhang、Richard R. Schrock、Amir H. Hoveyda

  DOI：10.1038/nature17396

  日期：2016.3.24

  halo-substituted molybdenum alkylidene species are exceptionally reactive and are able to participate in high-yielding olefin metathesis reactions that afford acyclic 1,2-disubstituted Z-alkenyl halides. Transformations are promoted by small amounts of a catalyst that is generated in situ and used with unpurified, commercially available and easy-to-handle liquid 1,2-dihaloethene reagents, and proceed to high

  烯烃复分解对现代有机化学产生了很大的影响，但仍然存在重要的缺点：例如，缺乏可用于生成无环烯基卤化物的有效工艺。卤代钌卡宾配合物分解迅速或提供低活性和/或最小的立体选择性，我们对相应的高氧化态系统的理解是有限的。在这里，我们展示了以前未知的卤代钼亚烷基物质具有异常的反应性，并且能够参与提供无环 1,2-二取代 Z-烯基卤化物的高产烯烃复分解反应。原位生成的少量催化剂可促进转化，并与未纯化、市售且易于处理的液体 1,2-二卤代乙烯试剂一起使用，并在四小时内在常温下进行高转化率。我们以高达 91% 的收率和完全的 Z 选择性获得了许多链烯基氯、溴化物和氟化物。该方法可用于轻松合成生物活性化合物，以及对复杂有机分子进行位点和立体选择性氟化。
• Production of Hydroxy Unsaturated Fatty Acids Using Crude Lipoxygenase Obtained from Infected Rice Plants
  作者：Tadahiro Kato、Tsutomu Watanabe、Toshifumi Hirukawa、Norihiro Tomita、Tsuneo Namai

  DOI：10.1246/bcsj.69.1663

  日期：1996.6

  In order to explore the oxidation mode of lipoxygenase (LOX) obtained from infected rice plants, typical unsaturated fatty acids (3—8) were treated with LOX and oxygen. It was observed that ω-10 and ω-6 positions of unsaturated fatty acids were oxidized predominantly in the cases of exotic ω-6 (4 and 5) and ω-3 (7 and 8) series, respectively. In the case of endogenous fatty acids (3 and 6), oxidation at ω-6 position predominated. All the allylic alcohols obtained by reduction of the oxidation products with NaBH4 possess S-configuration.

  为了探索从感染的水稻植物中获得的脂氧化酶（LOX）的氧化模式，通过LOX和氧气处理了典型的不饱和脂肪酸（3—8）。观察到在异源ω-6（4和5）和ω-3（7和8）系列的不饱和脂肪酸中，主要在ω-10和ω-6位发生氧化。而在内源性脂肪酸（3和6）的情况下，ω-6位的氧化占主导地位。通过用NaBH4还原氧化产物获得的所有烯丙醇均具有S构型。
• Epoxidation of carbon-carbon double bond with membrane bound peroxygenase
  申请人：Piazza George J.

  公开号：US06852315B2

  公开（公告）日：2005-02-08

  A method has been discovered for the epoxidation of a compound having at least one carbon-carbon double bond, the method involves reacting a compound having at least one carbon-carbon double bond, a solvent, an oxidant, and membrane bound peroxygenase. Also discovered is a method for preparing the membrane bound peroxygenase involving grinding seeds containing peroxygenase to produce ground seeds, homogenizing the ground seeds in a buffer to form a slurry, centrifuging the slurry to produce a first supernatant, centrifuging the first supernatant to produce a second supernatant, and filtering said second supernatant through a protein-binding membrane filter to produce membrane bound peroxygenase; optionally the second supernatant is filtered through a hydrophilic membrane filter prior to filtering the second supernatant through a protein-binding membrane filter.

  已发现一种用于环氧化至少含有一个碳-碳双键的化合物的方法，该方法涉及将至少含有一个碳-碳双键的化合物、溶剂、氧化剂和膜结合过氧化酶反应。还发现了一种制备膜结合过氧化酶的方法，包括研磨含有过氧化酶的种子以产生研磨后的种子，将研磨后的种子在缓冲液中均质化以形成混浊液，离心混浊液以产生第一上清液，离心第一上清液以产生第二上清液，并通过蛋白结合膜过滤器过滤所述第二上清液以产生膜结合过氧化酶；可选地，在将第二上清液通过蛋白结合膜过滤器过滤之前，将第二上清液通过亲水性膜过滤器过滤。
• An efficient synthesis of 13(S)-hydroxy-9Z,11E-octadecadienoic (coriolic) acid.
  作者：Robert Bloch、Marie-Thérèse Perfetti

  DOI：10.1016/0040-4039(90)80129-a

  日期：1990.1

  An efficient and highly selective total synthesis of 13(S)-hydroxy-9Z,11E octadecadienoic (coriolic) acid is described, starting from an optically active lactol easily available through an enantioselective enzymatic hydrolysis.

  描述了一种高效且高度选择性的13（S）-羟基-9Z，11E十八碳二烯酸（coolaolic）的全合成反应，该反应是从容易通过对映选择性酶水解获得的旋光性乳糖醇开始的。