2-(4-methoxybenzyl)succinonitrile

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-(4-methoxybenzyl)succinonitrile
• 英文别名: 2-[(4-Methoxyphenyl)methyl]butanedinitrile
• 化学式: C₁₂H₁₂N₂O
• 分子量: 200.24
• InChiKey: FUQPAUUPFKYMIP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  56.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (4-甲氧基苄基)-三甲基硅烷 、 反丁烯二腈 在 lithium perchlorate 作用下， 以 水 、 乙腈 为溶剂， 反应 24.0h， 以90%的产率得到2-(4-methoxybenzyl)succinonitrile
  参考文献：
  名称：

  Decatungstate As Photoredox Catalyst: Benzylation of Electron-Poor Olefins

  摘要：

  Excited tetrabutylammonium decatungstate (TBADT), known to activate a variety of compounds via hydrogen atom transfer (HAT), has now been applied as a photoredox catalyst for the effective oxidative cleavage of benzyl silanes and radical benzylation of reducible olefins occurring in isolated yields from poor to excellent.

  DOI：

  10.1021/ol301900p

文献信息

• Smooth Photocatalyzed Benzylation of Electrophilic Olefins via Decarboxylation of Arylacetic Acids
  作者：Luca Capaldo、Luca Buzzetti、Daniele Merli、Maurizio Fagnoni、Davide Ravelli

  DOI：10.1021/acs.joc.6b00984

  日期：2016.8.19

  Arylacetic acids were used as sources of benzyl radicals under tetrabutylammonium decatungstate photocatalyzed conditions for the benzylation of electron-poor olefins. The reaction proceeds smoothly in a mixed aqueous medium (MeCN/H2O 2/1) in the presence of NaHCO3, NaClO4, and an electron transfer agent (biphenyl). The reaction tolerates a wide variety of functional groups on the aromatic ring (whether

  在四丁基铵去癸酸盐光催化条件下，丙烯酸被用作苄基的来源，用于贫电子烯烃的苄基化。在NaHCO 3，NaClO 4和电子转移剂（联苯）的存在下，反应在混合水性介质（MeCN / H 2 O 2/1）中平稳进行。该反应可耐受芳环上的各种官能团（无论是供电子还是吸电子），并可扩展为杂芳族类似物。烯烃具有自由基陷阱和电子受体的双重作用。本方法还可扩展至芳基丙酸（包括非甾体抗炎药布洛芬和氟比洛芬），以及扁桃酸衍生物。
• TiO₂-photocatalyzed reactions of some benzylic donors
  作者：Laura Cermenati、Maurizio Fagnoni、Angelo Albini

  DOI：10.1139/v03-048

  日期：2003.6.1

  TiO₂-photocatalyzed oxidation of toluene (1a), benzyltrimethylsilane (1b), and 4-methoxybenzyltrimethylsilane (1c) has been carried out in acetonitrile under oxygen, under nitrogen, and in the presence of electrophilic alkenes under various conditions (using Ag₂SO₄ as electron acceptor, adding 2.5% H₂O, changing solvent to CH₂Cl₂). Benzyl radicals, formed via electron transfer and fragmentation, are trapped. A good material balance is often obtained. The overall efficiency of the process depends on the donor E_ox, on the rate of fragmentation of the radical cation, and on the acceptor present (Ag⁺ is an efficient oxidant, an electrophilic alkene a poor one, O₂ is intermediate). With ring-unsubstituted benzyl derivatives 1a and 1b, oxidative fragmentation occurs mainly close to the catalyst surface. The benzyl radicals form at a high local concentration and give benzaldehyde under O₂, bibenzyl under N₂ and dibenzylated derivatives by attack on the alkenes (acrylonitrile, fumaronitrile, maleic acid). In this case, using CH₂Cl₂–O₂ enhances the yield of benzaldehyde. With methoxylated 1c, however, the radical cation migrates into the solution before fragmentation and, therefore, the free benzyl radical is formed. This radical in part is oxidized to the cation, giving a considerable amount of benzylacetamide (or of the alcohol with water), and in part is trapped by the alkenes. The last reaction is less efficient in this case and yields monobenzyl derivatives.Key words: photocatalysis, oxidation, alkylation.

  TiO2光催化氧化甲苯（1a）、苄基三甲基硅烷（1b）和4-甲氧基苄基三甲基硅烷（1c）已在乙腈中在氧气下、在氮气下和在存在亲电烯烃的情况下进行，使用Ag2SO4作为电子受体，添加2.5％H2O，将溶剂改变为CH2Cl2等各种条件。通过电子转移和裂解形成的苄基自由基被捕获。通常可以得到良好的物质平衡。该过程的整体效率取决于给体Eox，自由基阳离子裂解速率以及存在的受体（Ag+是高效氧化剂，亲电烯烃是较差的，O2处于中间位置）。对于环未取代的苄衍生物1a和1b，氧化裂解主要发生在催化剂表面附近。苄基自由基在高局部浓度下形成，并在氧气下生成苯甲醛，在氮气下生成联苯，在攻击烯烃（丙烯腈、己二腈、马来酸）时生成二苄衍生物。在这种情况下，使用CH2Cl2-O2可以增加苯甲醛的产率。然而，对于甲氧基化的1c，自由基阳离子在裂解之前会迁移到溶液中，因此形成自由苄基自由基。这种自由基部分被氧化成阳离子，产生相当数量的苄基乙酰胺（或与水反应生成醇），部分被烯烃捕获。在这种情况下，最后一种反应效率较低，产生单苄基衍生物。关键词：光催化，氧化，烷基化。
• Synthetic Application of Bismuth LMCT Photocatalysis in Radical Coupling Reactions
  作者：Dominik Birnthaler、Rok Narobe、Eliseo Lopez-Berguno、Christoph Haag、Burkhard König

  DOI：10.1021/acscatal.2c05631

  日期：2023.1.20

  the activation and synthetic utilization of halides and other heteroatoms in metal complexes. Many metals are known to undergo LMCT but so far remain underutilized in the field of catalysis. A screening assay identifying LMCT activity helped us to expand this catalysis concept to the application of bismuth LMCT in organic radical coupling reactions. We demonstrate its application for the generation

  配体到金属电荷转移 (LMCT) 光催化可以激活和合成利用金属络合物中的卤化物和其他杂原子。已知许多金属会进行 LMCT，但迄今为止在催化领域仍未得到充分利用。鉴定 LMCT 活性的筛选试验帮助我们将这种催化概念扩展到铋 LMCT 在有机自由基偶联反应中的应用。我们展示了它在净氧化和氧化还原中性光化学反应中产生两种不同自由基（氯和羧基）的应用。对 Giese 型耦合模型的详细研究揭示了 BiCl 4 –和 BiCl 5 2–作为在 385 nm 照射下具有催化活性的铋物种。结合循环伏安法和紫外-可见研究，深入了解了高反应性铋 (II) 催化剂片段的反应性。
• Decatungstate Photocatalyzed Benzylation of Alkenes with Alkylaromatics
  作者：Hisham Qrareya、Davide Ravelli、Maurizio Fagnoni、Angelo Albini

  DOI：10.1002/adsc.201300598

  日期：2013.10.11

  AbstractThe direct benzylation of electrophilic alkenes with alkylbenzenes has been achieved by decatungstate photocatalysis in a high ionic strength medium (5:1 acetonitrile/water mixed solvents, 0.5 M lithium perchlorate). The reaction has been extended to ring‐substituted (Cl, F, CN) toluenes and further alkylbenzenes. Intramolecular selectivity (p‐cymene, 4‐methylanisole) and deuteration effects support the atom transfer character of the process that, however, requires a sufficient stabilization of the intermediate polar exciplex to occur. The reactivity of the decatungstate anion is compared with that of aromatic ketones, the benchmark of photochemical hydrogen/electron transfer processes.magnified image
• Decatungstate As Photoredox Catalyst: Benzylation of Electron-Poor Olefins
  作者：Sara Montanaro、Davide Ravelli、Daniele Merli、Maurizio Fagnoni、Angelo Albini

  DOI：10.1021/ol301900p

  日期：2012.8.17

  Excited tetrabutylammonium decatungstate (TBADT), known to activate a variety of compounds via hydrogen atom transfer (HAT), has now been applied as a photoredox catalyst for the effective oxidative cleavage of benzyl silanes and radical benzylation of reducible olefins occurring in isolated yields from poor to excellent.