3-(4-(苄氧基)-3,5-二甲氧基苯基)-3-羟基-2-(2-甲氧基苯氧基)丙酸乙酯 | 151541-15-0

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 中文名称: 3-(4-(苄氧基)-3,5-二甲氧基苯基)-3-羟基-2-(2-甲氧基苯氧基)丙酸乙酯
• 英文名称: ethyl 3-(4-(benzyloxy)-3,5-dimethoxyphenyl)-3-hydroxy-2-(2-methoxyphenoxy)propanoate
• 英文别名: ethyl 3-(3,5-dimethoxy-4-phenylmethoxyphenyl)-3-hydroxy-2-(2-methoxyphenoxy)propanoate
• CAS: 151541-15-0
• 化学式: C₂₇H₃₀O₈
• 分子量: 482.53
• InChiKey: HZDAVWPNTDXBJO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  35
• 可旋转键数：
  13
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  92.7
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  3-(4-(苄氧基)-3,5-二甲氧基苯基)-3-羟基-2-(2-甲氧基苯氧基)丙酸乙酯 在 sodium tetrahydroborate 、 甲酸 、 (4,4'-di-tert-butyl-2,2'-dipyridyl)-bis-(2-phenylpyridine(-1H))-iridium(III) hexafluorophosphate 、 五甲基苯 、 C₂₆H₅₁N₂O₂⁽¹⁺⁾*BF₄^(1-) 、 silica gel 、 三氯化硼 、 potassium carbonate 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 二甲基亚砜 、 丙酮 、 乙腈 为溶剂， 反应 79.0h， 生成 3-羟基-2-(2-甲氧基苯氧基)-1-(4-甲氧基苯基)丙基-1-酮
  参考文献：
  名称：

  A Photochemical Strategy for Lignin Degradation at Room Temperature

  摘要：

  The development of a room-temperature lignin degradation strategy consisting of a chemoselective benzylic oxidation with a recyclable oxidant ([4-AcNH-TEMPO]BF4) and a catalytic reductive C-O bond cleavage utilizing the photocatalyst [Ir(ppy)(2)(dtbbpy)]PF6 is described. This system was tested on relevant lignin model substrates containing beta-O-4 linkages to generate fragmentation products in good to excellent yields.

  DOI：

  10.1021/ja4113462
• 作为产物：
  描述：

  丁香醛 在 四丁基溴化铵 、 sodium chloride 、 sodium hydroxide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 水 、 甲苯 为溶剂， 反应 5.17h， 生成 3-(4-(苄氧基)-3,5-二甲氧基苯基)-3-羟基-2-(2-甲氧基苯氧基)丙酸乙酯
  参考文献：
  名称：

  一氧化氮和肼对木质素系统的顺序裂解

  摘要：

  代表性木质素系统的裂解已在无金属的两步骤序列中完成，首先使用一氧化氮进行氧化，然后使用肼进行还原性C-O键断裂。通过将一氧化氮和木质素结合在一起，新开发的增值策略显示了从两种废料开始的特殊特征，并且它进一步利用了Wolff-Kishner还原的引人注目的条件首次将C-O键裂解。

  DOI：

  10.1002/adsc.201901641

文献信息

• Chemoselective Metal-Free Aerobic Alcohol Oxidation in Lignin
  作者：Alireza Rahimi、Ali Azarpira、Hoon Kim、John Ralph、Shannon S. Stahl

  DOI：10.1021/ja401793n

  日期：2013.5.1

  An efficient organocatalytic method for chemoselective aerobic oxidation of secondary benzylic alcohols within lignin model compounds has been identified. Extension to selective oxidation in natural lignins has also been demonstrated. The optimal catalyst system consists of 4-acetamido-TEMPO (5 mol %; TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) in combination with HNO3 and HCl (10 mol % each). Preliminary

  已经确定了一种有效的有机催化方法，用于对木质素模型化合物中的仲苄醇进行化学选择性有氧氧化。天然木质素中选择性氧化的扩展也已被证明。最佳催化剂体系由 4-乙酰氨基-TEMPO（5 mol%；TEMPO = 2,2,6,6-四甲基哌啶-N-氧基）与 HNO3 和 HCl（各 10 mol%）组成。初步研究强调了将该方法与随后的氧化步骤相结合以实现 CC 键断裂的前景。
• Photocatalytic Oxidation of Lignin Model Systems by Merging Visible-Light Photoredox and Palladium Catalysis
  作者：Markus D. Kärkäs、Irene Bosque、Bryan S. Matsuura、Corey R. J. Stephenson

  DOI：10.1021/acs.orglett.6b02651

  日期：2016.10.7

  Two-step oxidation/reduction strategies, whereby the first oxidation step is required to “activate” lignin systems for controlled fragmentation reactions, have recently emerged as viable routes toward this goal. Herein we describe a catalytic protocol for oxidation of lignin model systems by combining photoredox and Pd catalysis. The developed dual catalytic protocol allowed the efficient oxidation of lignin

  长期以来，木质素增值一直被认为是可再生生产芳香族化合物的可持续解决方案。最近已经出现了两步氧化/还原策略，即第一步氧化需要“激活”木质素系统以进行受控的片段化反应，是实现该目标的可行途径。本文中，我们描述了通过结合光氧化还原和Pd催化作用来氧化木质素模型系统的催化方案。发达的双重催化方案允许木质素模型底物在室温下有效氧化，从而以良好或优异的收率提供氧化产物。
• Chemoselective oxidant-free dehydrogenation of alcohols in lignin using Cp*Ir catalysts
  作者：Rui Zhu、Bing Wang、Minshu Cui、Jin Deng、Xinglong Li、Yingbo Ma、Yao Fu

  DOI：10.1039/c5gc02347e

  日期：——

  Hydrogen gas was captured from native lignin using the catalyst Cp*Ir and the dehydrogenative lignin could be further degraded with the help of Zn & NH4Cl through a two-step one pot process.

  使用催化剂Cp * Ir从天然木质素中捕获氢气，脱氢木质素可借助Zn＆NH 4 Cl通过两步一锅法进一步降解。
• Electroorganic reactions. 38. Mechanism of electrooxidative cleavage of lignin model dimers
  作者：Vera L. Pardini、Carmen Z. Smith、James H. P. Utley、Reinaldo R. Vargas、Hans Viertler

  DOI：10.1021/jo00026a022

  日期：1991.12

  The mechanisms for oxidative cleavage of several phenolic ethers, models for lignins, have been investigated by a detailed comparison of the result of anodic oxidation at nickel anodes in alkaline electrolyte with that of oxidation in acetonitrile in the presence of a triarylamine redox catalyst. The latter reaction is unambiguously initiated by single-electron transfer (SET), and in this case the major product of cleavage is aldehyde (vanillin or syringaldehyde derivatives). At nickel anodes polymerization is predominant although the aldehydes are formed together with larger amounts of the corresponding carboxylic acids. Combinations of 4-hydroxyl, alpha-keto, beta-O-aryl, and beta-hydroxymethyl functionality are shown to be crucial for the oxidation at nickel; the carboxylic acid formation probably involves a route with initial hydrogen atom abstraction at the surface. Important chemical conversions precede and accompany oxidation in alkaline media, and these are associated with the propensity for polymerization.
• Cross-Coupling of Hydroxycinnamyl Aldehydes into Lignins
  作者：Hoon Kim、John Ralph、Nabila Yahiaoui、Michel Pean、Alain-M. Boudet

  DOI：10.1021/ol005906o

  日期：2000.7.1

  [GRAPHICS]Pathways for hydroxycinnamyl aldehyde incorporation into lignins are revealed by examining transgenic plants deficient in cinnamyl alcohol dehydrogenase, the enzyme that converts hydroxycinnamyl aldehydes to the hydroxycinnamyl alcohol lignin monomers. In such plants the aldehydes incorporate into lignins via radical coupling reactions. As diagnostically revealed by long-range C-13-H-1 correlative NMR, sinapyl aldehyde (3,5-dimethoxy 4-hydroxy-cinnamaldehyde) 8-O-4-cross-couples with both gualacyl (3-methoxy-4-hydroxyphenyl-propanoid) and syringyl (3,5-dimethoxy-4-hydroxyphenyl-propanoid) units, whereas coniferyl aldehyde cross-couples only with syringyl units.