1-(4-(benzyloxy)-3,5-dimethoxyphenyl)-3-hydroxy-2-(2-methoxyphenoxy)propan-1-one | 535967-82-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(4-(benzyloxy)-3,5-dimethoxyphenyl)-3-hydroxy-2-(2-methoxyphenoxy)propan-1-one
• CAS: 535967-82-9
• 化学式: C₂₅H₂₆O₇
• 分子量: 438.477
• InChiKey: MZDZQNOFCBGQMX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.91
• 重原子数：
  32.0
• 可旋转键数：
  11.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  83.45
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  1-(4-(benzyloxy)-3,5-dimethoxyphenyl)-3-hydroxy-2-(2-methoxyphenoxy)propan-1-one 在 甲酸 、 (4,4'-di-tert-butyl-2,2'-dipyridyl)-bis-(2-phenylpyridine(-1H))-iridium(III) hexafluorophosphate 、 五甲基苯 、 三氯化硼 、 potassium carbonate 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 二甲基亚砜 、 丙酮 、 乙腈 为溶剂， 反应 55.0h， 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：

  1-(4-(苄氧基)-3,5-二甲氧基苯基)-2(2-甲氧基苯氧基)丙烷-1,3-二醇 在 C₂₆H₅₁N₂O₂⁽¹⁺⁾*BF₄^(1-) 、 silica gel 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以94%的产率得到1-(4-(benzyloxy)-3,5-dimethoxyphenyl)-3-hydroxy-2-(2-methoxyphenoxy)propan-1-one
  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

文献信息

• Visible light mediated reductions of ethers, amines and sulfides
  作者：Timothy M. Monos、Gabriel Magallanes、Leanne J. Sebren、Corey R.J. Stephenson

  DOI：10.1016/j.jphotochem.2016.05.014

  日期：2016.9

  Visible light-mediated photoredox catalysis enables the chemoselective reduction of activated carbon–heteroatom bonds as a function of reduction potential. The expansion of the scope of C–X bond reductions towards less activated motifs, such as ethers, amines and sulfides, is important to both organic synthesis and macromolecular degradation method development. In the present report, exploration of

  可见光介导的光氧化还原催化作用使活性炭-杂原子的化学选择性还原成为还原电位的函数。将C–X键还原的范围扩展至活化程度较低的基序，例如醚，胺和硫化物，对于有机合成和大分子降解方法的开发均至关重要。在本报告中，探索在醇类溶剂中进行光氧化还原催化可减少i Pr 2 NEt和HCO 2 H在超化学计量中减少α-酮醚，胺和硫化物的使用。另外，在不存在断裂的情况下，提供了C C键的形成，表明在这些转化中存在中间的酮基。
• Domino lignin depolymerization and reconnection to complex molecules mediated by boryl radicals
  作者：Longcheng Hong、Astrid Spielmeyer、Janin Pfeiffer、Hermann A. Wegner

  DOI：10.1039/d0cy00558d

  日期：——

  Herein, we present a new transition metal free degradation procedure utilizing DDQ-oxidation and boryl radical mediated degradation, followed by reconnection of a monomer intermediate to a new dimer in a domino process. Our results include the selective degradation of oxidized β-O-4 model compounds by a boryl radical initiated with a catalytic amount of 4-(4-pyridinyl)benzonitrile and bispinacolborane

  木质素的化学降解由于具有从可再生资源生产化学药品的潜力，因此引起了越来越多的关注。在这里，我们介绍了一种利用DDQ氧化和硼基自由基介导的降解的新的无过渡金属的自由降解程序，然后在多米诺工艺中将单体中间体重新连接至新的二聚体。我们的结果包括通过催化量为4-（4-吡啶基）苄腈和双spinacolborane B 2（pin）2引发的硼基选择性降解氧化的β-O-4模型化合物。以及其在有机溶剂木质素中的应用 通过将过程中的键形成转变纳入工艺过程，此顺序过程将木质素降解的工具箱从简单的解聚扩展为高价值产品，还提供了一种新型的无过渡金属的方法来构建1,6-二酮片段。
• CsPbBr₃ Quantum Dots Promoted Depolymerization of Oxidized Lignin via Photocatalytic Semi‐Hydrogenation/Reduction Strategy
  作者：Huating Jiang、Minxia Liu、Xiao Lian、Mingxiang Zhu、Fang Zhang

  DOI：10.1002/anie.202318850

  日期：2024.2.12

  Due to the demanding depolymerization conditions and limited catalytic efficiency, enhancing lignin valorization remains challenging. Therefore, lowering the bond dissociation energy (BDE) has emerged as a viable strategy for achieving mild yet highly effective cleavage of bonds. In this study, a photocatalytic semi‐hydrogenation/reduction strategy utilizing CsPbBr₃ quantum dots (CPB‐QDs) and Hantzsch ester (HEH₂) as a synergistic catalytic system was introduced to reduce the BDE of C_β−O−Ar, achieving effective cleavage of the C_β−O−Ar bond. This strategy offers a wide substrate scope encompassing various β‐O‐4 model lignin dimers, preoxidized β‐O‐4 polymers, and native oxidized lignin, resulting in the production of corresponding ketones and phenols. Notably, this approach attained a turnover frequency (TOF) that is 17 times higher than that of the reported Ir‐catalytic system in the photocatalytic depolymerization of the lignin model dimers. It has been observed via meticulous experimentation that HEH₂ can be activated by CPB‐QDs via single electron transfer (SET), generating HEH₂⋅⁺ as a hydrogen donor while also serving as a hole quencher. Moreover, HEH₂⋅⁺ readily forms an active transition state with the substrates via hydrogen bonding. Subsequently, the proton‐coupled electron transfer (PCET) from HEH₂⋅⁺ to the carbonyl group of the substrate generates a C_α⋅ intermediate.

  摘要由于苛刻的解聚条件和有限的催化效率，提高木质素的价值仍具有挑战性。因此，降低键解离能（BDE）已成为实现温和而高效的键裂解的可行策略。本研究采用了一种光催化半氢化/还原策略，利用 CsPbBr3 量子点（CPB-QDs）和汉茨酯（HEH2）作为协同催化系统，降低 Cβ-O-Ar 的 BDE，从而实现 Cβ-O-Ar 键的有效裂解。这种策略提供了广泛的底物范围，包括各种 β-O-4 模型木质素二聚体、预氧化的 β-O-4 聚合物和原生氧化木质素，从而产生相应的酮和酚。值得注意的是，在木质素模型二聚体的光催化解聚过程中，这种方法达到的周转频率（TOF）是已报道的铱催化系统的 17 倍。通过细致的实验观察发现，CPB-QDs 可通过单电子转移（SET）激活 HEH2，生成 HEH2⋅+ 作为氢供体，同时还可作为空穴淬灭剂。此外，HEH2⋅+ 很容易通过氢键与底物形成活性过渡态。随后，质子耦合电子转移（PCET）从 HEH2⋅+ 到底物的羰基，生成 Cα⋅ 中间体。