7-Oxomatairesinol | 53250-61-6

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 呋喃类木脂素
• 英文名称: 7-Oxomatairesinol
• 英文别名: (2R,3R)-3-(4-hydroxy-3-methoxybenzoyl)-2-(4-hydroxy-3-methoxybenzyl)-4-butanolide；lignan oxo-matairesinol；(+)-oxomatairesinol；ketomatairesinol；oxomatairesinol；(3R,4R)-4-(4-hydroxy-3-methoxybenzoyl)-3-[(4-hydroxy-3-methoxyphenyl)methyl]oxolan-2-one
• CAS: 53250-61-6
• 化学式: C₂₀H₂₀O₇
• 分子量: 372.375
• InChiKey: VBBXDTGECAKSAY-KGLIPLIRSA-N

物化性质

• 熔点：
  74-76 °C
• 沸点：
  641.5±55.0 °C(Predicted)
• 密度：
  1.347±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  102
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  (7R,8R,8'R)-(-)-7-allo-hydroxymatairesinol 在 spherical alumina nanoparticle-supported gold 作用下， 以 水 、 异丙醇 为溶剂， 70.0 ℃ 、101.33 kPa 条件下， 反应 4.0h， 生成 7-Oxomatairesinol
  参考文献：
  名称：

  氧气辅助的羟基麦角甾醇脱氢：金催化剂上的选择性仲醇氧化

  摘要：

  在Au / Al 2 O 3催化剂上研究了生物质衍生的木脂素羟基羟甲基麦甾醇（HMR）选择性脱氢成氧代松香树脂醇（oxoMAT）。该反应在343 K的半间歇式玻璃反应器中，在两种不同的气体气氛下进行，即通过合成空气或氮气进行生产。实际上，所研究的反应是在Au催化剂上进行仲醇氧化的一个例子。因此，研究的HMR氧化脱氢反应机理对于基本了解Au表面的其他仲醇脱氢很有用。为了研究决定HMR向oxoMAT脱氧和氧辅助脱氢的基本催化步骤，将反应在真空下于Au 28上模拟簇。还在DFT层面上研究了所涉及的分子物种O 2的吸附，三种不同的HMR非对映异构体（即一种SRR和两种RRR形式）以及oxoMAT衍生物的吸附。特别是Au 28上SRR- HMR和RRR- HMR非对映异构体的能级和结构差异根据在有氧或无氧条件下发生的HMR脱氢的不同反应途径，对簇进行了分析。相应的机制解释了实验观察到的氧气辅助反应的

  DOI：

  10.1002/chem.201202957

文献信息

• Radical Carboxyarylation Approach to Lignans. Total Synthesis of (−)-Arctigenin, (−)-Matairesinol, and Related Natural Products
  作者：Joshua Fischer、Aaron J. Reynolds、Lisa A. Sharp、Michael S. Sherburn

  DOI：10.1021/ol049878b

  日期：2004.4.1

  of seven biologically important lignan natural products, including (-)-arctigenin, (-)-matairesinol, and (-)-alpha-conidendrin, by way of a highly stereoselective domino radical sequence is presented. The reported stereochemistry of the natural product 7-hydroxyarctigenin is shown to be erroneous; a diastereoisomeric structure is assigned to the natural product.

  [反应：见正文]通过高度立体选择性的多米诺基自由基序列，提出了7种具有重要生物学意义的木脂素天然产物的总合成物，包括（-）-arctigenin，（-）-matairesinol和（-）-alpha-conidendrin。据报道，天然产物7-羟基arctigenin的立体化学是错误的。非对映异构结构被分配给天然产物。
• Oxygen-Assisted Hydroxymatairesinol Dehydrogenation: A Selective Secondary-Alcohol Oxidation over a Gold Catalyst
  作者：Antonio Prestianni、Francesco Ferrante、Olga A. Simakova、Dario Duca、Dmitry Yu. Murzin

  DOI：10.1002/chem.201202957

  日期：2013.4.2

  catalyst. Thus, the investigated reaction mechanism of HMR oxidative dehydrogenation is useful for the fundamental understanding of other secondary‐alcohol dehydrogenation over Au surfaces. To investigate the elementary catalytic steps ruling both oxygen‐free‐ and oxygen‐assisted dehydrogenation of HMR to oxoMAT, the reactions were mimicked in a vacuum over an Au28 cluster. Adsorption of the involved molecular

  在Au / Al 2 O 3催化剂上研究了生物质衍生的木脂素羟基羟甲基麦甾醇（HMR）选择性脱氢成氧代松香树脂醇（oxoMAT）。该反应在343 K的半间歇式玻璃反应器中，在两种不同的气体气氛下进行，即通过合成空气或氮气进行生产。实际上，所研究的反应是在Au催化剂上进行仲醇氧化的一个例子。因此，研究的HMR氧化脱氢反应机理对于基本了解Au表面的其他仲醇脱氢很有用。为了研究决定HMR向oxoMAT脱氧和氧辅助脱氢的基本催化步骤，将反应在真空下于Au 28上模拟簇。还在DFT层面上研究了所涉及的分子物种O 2的吸附，三种不同的HMR非对映异构体（即一种SRR和两种RRR形式）以及oxoMAT衍生物的吸附。特别是Au 28上SRR- HMR和RRR- HMR非对映异构体的能级和结构差异根据在有氧或无氧条件下发生的HMR脱氢的不同反应途径，对簇进行了分析。相应的机制解释了实验观察到的氧气辅助反应的
• Radical and Superoxide Scavenging Activities of Matairesinol and Oxidized Matairesinol
  作者：Satoshi YAMAUCHI、Takuya SUGAHARA、Yuki NAKASHIMA、Akihiro OKADA、Koichi AKIYAMA、Taro KISHIDA、Masashi MARUYAMA、Toshiya MASUDA

  DOI：10.1271/bbb.60096

  日期：2006.8.23

  The radical and superoxide scavenging activities of oxidized matairesinols were examined. It could be assumed that the free benzylic position was important for higher radical scavenging activity. The different level of activity was observed between 7′-oxomatairesinol (Mat 2) and 7-oxomatairesinol (Mat 3). The activity of 8-hydroxymatairesinol was lower than that of matairesinol (Mat 1). The superoxide scavenging activity of the oxidized matairesinols was also demonstrated for the first time. It is assumed that the pKa value of phenol in the oxidized matairesinols affected this activity.

  研究了氧化马黛茶酚的自由基和超氧化物清除活性。可以推断，游离苄基位置对更高的自由基清除活性非常重要。7′-oxomatairesinol (Mat 2) 和 7-oxomatairesinol (Mat 3) 的活性水平不同。8-hydroxymatairesinol 的活性低于 matairesinol（Mat 1）。氧化马黛茶酚的超氧化物清除活性也是首次得到证实。据推测，氧化的马黛茶酚中苯酚的 pKa 值影响了这种活性。
• Oxidative dehydrogenation of a biomass derived lignan – Hydroxymatairesinol over heterogeneous gold catalysts
  作者：Olga A. Simakova、Elena V. Murzina、Päivi Mäki-Arvela、Anne-Riikka Leino、Betiana C. Campo、Krisztián Kordás、Stefan M. Willför、Tapio Salmi、Dmitry Yu. Murzin

  DOI：10.1016/j.jcat.2011.05.025

  日期：2011.8

  Synthesis of the lignan oxomatairesinol via oxidative dehydrogenation of the naturally occurring lignan hydroxymatairesinol was studied over gold catalysts supported on C, TiO2, SiO2, Al2O3, and MgO. In order to investigate the reaction performance over the gold catalyst, synthesis of lignan oxomatairesinol was carried out in different organic solvents/water mixtures under synthetic air and nitrogen atmosphere at 373 K, and using also isolated hydroxymatairesinol isomers as a starting material. The results were compared with those obtained over palladium catalysts. Synthesized supported gold catalysts as well as the corresponding supports were characterized by TEM, XRD, ICP-OES, CO2-TPD, FUR (using pyridine as a probe molecule), and XPS. Gold catalysts were shown to display superior performance compared with palladium ones: the activity was 4 times higher, with selectivity toward oxomatairesinol being 100%, while 60-85% were obtained over palladium catalysts. In contrast to palladium, the activity of gold catalysts is high in aerobic conditions and water-propan-2-ol mixture. However, activity and selectivity of gold catalysts were shown to be dependent on the electronic state of the metal and, similar to palladium catalysts, on the support acidity. (C) 2011 Elsevier Inc. All rights reserved.
• Oxidative transformation of the natural lignan hydroxymatairesinol with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
  作者：Patrik C Eklund、Rainer E Sjöholm

  DOI：10.1016/s0040-4020(03)00683-5

  日期：2003.6

  The oxidative transformation of the two isomers of the natural lignan hydroxymatairesinol from Norway Spruce (Picea abies) by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), has been studied. Significant differences in the outcome of the reactions were observed when the pure isomers of hydroxymatairesinol were reacted with DDQ under the same conditions. The different stereoelectronic effects in the two isomers as well as their conformational structures seem to determine the site of reaction, which results in different reaction products. Several products were identified by GC-MS and NMR spectroscopy. Oxomatairesinol was obtained in a yield of 25%. (C) 2003 Elsevier Science Ltd. All rights reserved.