(E)-tert-butyl 3-(2,4-difluorophenyl)acrylate

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (E)-tert-butyl 3-(2,4-difluorophenyl)acrylate
• 英文别名: tert-butyl (2E)-3-(2,4-difluorophenyl)-2-propenoate；tert-butyl (E)-3-(2',4'-difluorophenyl)prop-2-enoate；3-(2,4-difluorophenyl)acrylic acid tert-butyl ester；tert-butyl (2E)-3-(2,4-difluorophenyl)prop-2-enoate；tert-butyl (E)-3-(2,4-difluorophenyl)prop-2-enoate
• 化学式: C₁₃H₁₄F₂O₂
• 分子量: 240.25
• InChiKey: FINSXUPWDMWKHQ-FNORWQNLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E)-tert-butyl 3-(2,4-difluorophenyl)acrylate 在 正丁基锂 、 Pd(OH)2/C (6% w/w) 、 氢气 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 为溶剂， -78.0~20.0 ℃ 、506.66 kPa 条件下， 反应 26.5h， 生成 tert-butyl (S)-3-amino-3-(2',4'-difluorophenyl)propanoate
  参考文献：
  名称：

  Asymmetric synthesis of β-fluoroaryl-β-amino acids

  摘要：

  The conjugate addition of lithium (R)-N-benzyl-N-(alpha-methylbenzyl)amide to a range of beta-fluoroaryl-alpha,beta-unsaturated esters gave the corresponding beta-amino esters with high diastereoselectivity and in good isolated yields. Sequential treatment of the resultant beta-fluoroaryl-beta-amino esters under optimised hydrogenolysis conditions, followed by ester hydrolysis with 2.0 M aq HCl, provided access to a range of beta-fluoroaryl-beta-amino acids in good yield. (c) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.07.001
• 作为产物：
  描述：

  二乙基膦酰基乙酸叔丁酯 、 2,4-二氟苯甲醛 在 甲基溴化镁 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 15.25h， 以89%的产率得到(E)-tert-butyl 3-(2,4-difluorophenyl)acrylate
  参考文献：
  名称：

  Asymmetric synthesis of β-fluoroaryl-β-amino acids

  摘要：

  The conjugate addition of lithium (R)-N-benzyl-N-(alpha-methylbenzyl)amide to a range of beta-fluoroaryl-alpha,beta-unsaturated esters gave the corresponding beta-amino esters with high diastereoselectivity and in good isolated yields. Sequential treatment of the resultant beta-fluoroaryl-beta-amino esters under optimised hydrogenolysis conditions, followed by ester hydrolysis with 2.0 M aq HCl, provided access to a range of beta-fluoroaryl-beta-amino acids in good yield. (c) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.07.001

文献信息

• A convenient, efficient and reusable N-heterocyclic carbene-palladium(<scp>ii</scp>) based catalyst supported on magnetite for Suzuki–Miyaura and Mizoroki–Heck cross-coupling reactions
  作者：Vishal Kandathil、Bradley D. Fahlman、B. S. Sasidhar、Shivaputra A. Patil、Siddappa A. Patil

  DOI：10.1039/c7nj01876b

  日期：——

  NO2-NHC-Pd@Fe3O4 nanomagnetic catalyst showed excellent catalytic activity in both Suzuki–Miyaura and Mizoroki–Heck cross-coupling reactions for various substrates under mild reaction conditions. Recovery of the NO2-NHC-Pd@Fe3O4 nanomagnetic catalyst from the reaction mixture was easily accomplished by applying an external magnet. The recovered NO2-NHC-Pd@Fe3O4 nanomagnetic catalyst exhibited very good catalytic

  在目前的工作中，一种新型的磁性纳米颗粒负载的N-杂环卡宾-钯（II）（NO 2 -NHC-Pd @ Fe 3 O 4）纳米磁性催化剂是通过在有氧条件下使用廉价的化学药品通过简便的多步合成法合成的。NO 2 -NHC-Pd @ Fe 3 O 4纳米磁性催化剂通过各种分析技术进行了表征，例如衰减全反射红外光谱（ATR-IR），电感耦合等离子体原子发射光谱（ICP-AES），能量色散X射线光谱（EDS），场发射扫描电子显微镜（FESEM），透射电子显微镜（TEM），X射线粉末衍射（XRD），热重分析（TGA）和Brunauer–Emmett–Teller表面积分析（BET）。合成的NO 2 -NHC-Pd @ Fe 3 O 4纳米磁性催化剂在轻度反应条件下，在各种基材的Suzuki-Miyaura和Mizoroki-Heck交叉偶联反应中均表现出出色的催化活性。NO 2 -NHC-Pd @ Fe
• Non‐Chelate‐Assisted Palladium‐Catalyzed Aerobic Oxidative Heck Reaction of Fluorobenzenes and Other Arenes: When Does the C−H Activation Need Help?
  作者：Francisco Villalba、Ana C. Albéniz

  DOI：10.1002/adsc.202100677

  日期：2021.10.19

  sole oxidant and no redox mediator. Arenes with either electron-donating or electron-withdrawing groups can be functionalized in this way. Experimental data on the reaction with toluene as the model arene shows that the C−H activation step is turnover limiting and that the ligand structure is crucial to facilitate the reaction, which supports the involvement of the pyridone fragment in the C−H activation

  配体中的吡啶酮片段 [2, 2'-联吡啶]-6(1 H)-one (bipy-6-OH) 使简单芳烃与氧作为唯一氧化剂且无氧化还原介体发生氧化 Heck 反应。具有给电子或吸电子基团的芳烃可以通过这种方式进行功能化。与甲苯作为模型芳烃反应的实验数据表明，CH 活化步骤是周转限制，配体结构对于促进反应至关重要，这支持吡啶酮片段参与 CH 活化步骤。在氟芳烃的情况下，单和 1,2-二氟苯的烯基化需要 bipy-6-OH 的存在。相比之下，这种配体对 1,3-二氟、三、四和五氟苯的烯基化是有害的，这可以仅使用 [Pd(OAc) 2]。这与氟代芳烃的酸度有关，最酸性的酸经历更容易的 CH 活化，因此反应的其他步骤（例如烯烃的配位插入）对于多氟化芳烃在动力学上变得重要。在所有这些反应中，仅使用催化量的钼酸钠作为碱被证明是最佳的。
• The synthesis of enantiomerically pure, symmetrically substituted cyclopropane phosphonic acids — A constrained analog of the GABA antagonist phaclophen
  作者：Stephen Hanessian、Louis-David Cantin、Stéphan Roy、Daniele Andreotti、Arthur Gomtsyan

  DOI：10.1016/s0040-4039(96)02518-x

  日期：1997.2

  The stereocontrolled conjugate addition of anions derived from chiral α-chlorophosphonamides to α,β-unsaturated esters leads to the corresponding 3-chloro ester adducts which undergo intramolecular expulsion of the chlorine atom to give the corresponding cyclopropanes.

  衍生自手性α-氯膦酰胺的阴离子到α，β-不饱和酯的立体控制共轭加成反应导致相应的3-氯酯加合物发生分子内的氯原子排出，从而得到相应的环丙烷。
• Pd(OAc)₂ Catalyzed Olefination of Highly Electron-Deficient Perfluoroarenes
  作者：Xingang Zhang、Shilu Fan、Chun-Yang He、Xiaolong Wan、Qiao-Qiao Min、Jie Yang、Zhong-Xing Jiang

  DOI：10.1021/ja908434e

  日期：2010.4.7

  An efficient, Pd(OAc)(2) catalyzed method for direct olefination of highly electron-deficient perfluoroarenes was developed. The reaction scope includes a series of activated and nonactivated alkenes in moderate to high yields with moderate to high regio- and stereoselectivities.
• Asymmetric synthesis of β-fluoroaryl-β-amino acids
  作者：Stephen G. Davies、Ai M. Fletcher、Linlu Lv、Paul M. Roberts、James E. Thomson

  DOI：10.1016/j.tetasy.2012.07.001

  日期：2012.6

  The conjugate addition of lithium (R)-N-benzyl-N-(alpha-methylbenzyl)amide to a range of beta-fluoroaryl-alpha,beta-unsaturated esters gave the corresponding beta-amino esters with high diastereoselectivity and in good isolated yields. Sequential treatment of the resultant beta-fluoroaryl-beta-amino esters under optimised hydrogenolysis conditions, followed by ester hydrolysis with 2.0 M aq HCl, provided access to a range of beta-fluoroaryl-beta-amino acids in good yield. (c) 2012 Elsevier Ltd. All rights reserved.