ethyl (E)-2-fluoro-3-phenylacrylate | 20397-58-4

• 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: ethyl (E)-2-fluoro-3-phenylacrylate
• 英文别名: (E)-ethyl 2-fluoro-3-phenyl-2-propenoate；ethyl (E)-2-fluoro-3-phenyl-2-propenoate；(E)-ethyl-2-fluoro-3-phenyl propenoate；(E)-Ethyl 3-phenyl-2-fluoropropenate；(E)-ethyl 2-fluoro-3-phenylacrylate；ethyl 2-fluoro-3-phenylacrylate；ethyl (E)-2-fluoro-3-phenylprop-2-enoate
• CAS: 20397-58-4
• 化学式: C₁₁H₁₁FO₂
• 分子量: 194.206
• InChiKey: YLDYYTGJNSYKME-CSKARUKUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl (E)-2-fluoro-3-phenylacrylate 在 二异丁基氢化铝 作用下， 以 四氢呋喃 、 吡啶 、 甲苯 为溶剂， 生成 (E)-2-fluoro-3-phenylprop-2-enyl acetate
  参考文献：
  名称：

  Iridium-Catalyzed Asymmetric Hydrogenation of Fluorinated Olefins Using N,P-Ligands:  A Struggle with Hydrogenolysis and Selectivity

  摘要：

  To broaden the substrate scope of asymmetric iridium-catalyzed hydrogenation, fluorine-functionalized olefins were synthesized and hydrogenated with iridium complexes. Preliminary results showed high levels of fluorine elimination together with low selectivity. The loss of vinylic fluorine at first seemed difficult to handle, but further studies revealed that a catalyst with an azanorbornyl scaffold in the ligand gave more promising results. With this in mind, a new ligand was developed. This gave among the best results published to date for fluorine asymmetric hydrogenation, yielding high conversion and very high ee's with very little fluorine elimination. Further increasing the selectivity, the trials also revealed that tetrasubstituted fluorine-containing olefins can be hydrogenated with high ee's, despite that this class of compounds has usually shown low reactivity in this reaction type.

  DOI：

  10.1021/ja0686763
• 作为产物：
  描述：

  triethyl 2-fluoro-3-oxo-2-phosphono-3-phenylpropanoate 在 sodium tetrahydroborate 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 ethyl (E)-2-fluoro-3-phenylacrylate
  参考文献：
  名称：

  Acylation of fluorocarbethoxy-substituted ylides: a simple and general route to .alpha.-fluoro .beta.-keto esters

  摘要：

  (Fluorocarbethoxymethylene)tri-n-butylphosphorane (3) reacts with acid chlorides and anhydrides to form the corresponding carbon acylated phosphonium salts 4, and hydrolysis of 4 under mild basic conditions provides RCOCFHCOOEt (8) in moderate yields. The reaction is applicable to primary, secondary, tertiary, cyclic, aromatic, and ester-substituted acid chlorides. Acylation with ethyl chloroformate and ethyl chlorothioformate leads to the diesters CFH(COOEt)2 and EtSCOCFHCOOEt. Extension of this reaction sequence to perfluorinated and partially fluorinated acid chlorides did not proceed cleanly to give the expected phosphonium salts. However, the anion derived from (EtO)2P(O)CFHC(O)OEt reacts with R(F)COCl to form the corresponding C-acylated phosphonates 10, and hydrolysis of 10 gives R(F)COCFHCOOEt.

  DOI：

  10.1021/jo00001a052

文献信息

• Stereoselective Synthesis of Fluoroalkenoates and Fluorinated Isoxazolidinones: N-Substituents Governing the Dual Reactivity of Nitrones
  作者：G. K. Surya Prakash、Zhe Zhang、Fang Wang、Martin Rahm、Chuanfa Ni、Marc Iuliucci、Ralf Haiges、George A. Olah

  DOI：10.1002/chem.201303509

  日期：2014.1.13

  α‐Fluoroalkenoates and 4‐fluoro‐5‐isoxazolidinones are of vast interest due to their potential biological applications. We now demonstrate the syntheses of (E)‐α‐fluoroalkenoates and 4‐fluoro‐5‐isoxazolidinones by the reactions between nitrones and α‐fluoro‐α‐bromoacetate. By altering N‐substituents in nitrones, (E)‐α‐fluoroalkenoates and 4‐fluoro‐5‐isoxazolidinones can be achieved, respectively, with

  α-氟链烯酸酯和4-氟-5-异恶唑烷酮因其潜在的生物学应用而备受关注。现在，我们通过硝酮与α-氟代-α-溴乙酸酯之间的反应证明（E）-α-氟代链烯酸酯和4-氟代-5-异恶唑烷酮的合成。通过改变硝酮中的N-取代基，可以实现高化学选择性和立体选择性，分别获得（E）-α-氟代链烯酸酯和4-氟-5-异恶唑烷酮。已经进行了实验和计算研究以阐明反应机理。线性自由能关系研究进一步表明，N取代基效应主要是电子起源的。
• Modified Julia Fluoroolefination:  Selective Preparation of Fluoroalkenoates
  作者：Emmanuel Pfund、Cyril Lebargy、Jacques Rouden、Thierry Lequeux

  DOI：10.1021/jo070994c

  日期：2007.10.1

  The modified Julia olefination reaction has been applied to develop a stereoselective synthesis of fluoroalkenoate derivatives from a fluorobenzothiazolyl sulfone and aldehydes or a ketone. The olefination reaction can be achieved by using a variety of bases. DBU and DBU in the presence of MgBr2 were found to be the most efficient systems to prepare either (Z)- or (E)-alkenoates in moderate to excellent

  改性的朱莉娅烯化反应已用于开发从氟苯并噻唑基砜和醛或酮的氟代链烯酸酯衍生物的立体选择性合成。可以通过使用多种碱来实现烯化反应。发现在MgBr 2存在下，DBU和DBU是制备中度至优异的立体选择性的（Z）-或（E）-链烯酸酯的最有效系统。
• P[N(<i>i-</i>Bu)CH₂CH₂]₃N: Nonionic Lewis Base for Promoting the Room-Temperature Synthesis of α,β-Unsaturated Esters, Fluorides, Ketones, and Nitriles Using Wadsworth−Emmons Phosphonates
  作者：Venkat Reddy Chintareddy、Arkady Ellern、John G. Verkade

  DOI：10.1021/jo1012515

  日期：2010.11.5

  serves as an effective promoter for the room-temperature stereoselective synthesis of α,β-unsaturated esters, fluorides, and nitriles from a wide array of aromatic, aliphatic, heterocyclic, and cyclic aldehydes and ketones, using a range of Wadsworth−Emmons (WE) phosphonates. Among the analogues of 1c [R = Me (1a), i-Pr (1b), Bn (1d)], 1a and 1b performed well, although longer reaction times were involved

  双环三氨基膦P（RNCH 2 CH 2）3 N（R = i -Bu，1c）可作为室温下立体选择性合成α，β-不饱和酯，氟化物和腈的有效促进剂芳香族，脂肪族，杂环和环状醛和酮，使用一系列Wadsworth-Emmons（WE）膦酸酯。在1c [R = Me（1a），i -Pr（1b），Bn（1d）]的类似物中，1a和1b表现良好，尽管涉及的反应时间更长，而1d导致的收率低于1c。氰基，氯，溴，甲氧基，氨基，酯和硝基等官能团的耐受性很好。我们能够分离和表征（通过X射线；见上文）由2b和1c形成的反应性WE中间体。
• The One-Pot Wittig Reaction: A Facile Synthesis of α,β-Unsaturated Esters and Nitriles by Using Nanocrystalline Magnesium Oxide
  作者：Boyapati M. Choudary、Koosam Mahendar、M. Lakshmi Kantam、Kalluri V. S. Ranganath、Taimur Athar

  DOI：10.1002/adsc.200606001

  日期：2006.9

  Nanocrystalline magnesium oxide was found to be an effective heterogeneous, solid base catalyst for the one-pot Wittig reaction to afford α,β-unsaturated esters and nitriles in excellent yields with high E-stereoselectivity in the presence of triphenylphosphine under mild conditions.

  发现纳米晶氧化镁是一种有效的非均相，固态碱催化剂，可在一锅Wittig反应中以温和条件在三苯基膦存在下以高收率和高E-立体选择性以优异的产率提供α，β-不饱和酯和腈。
• A Facile and Mild Approach for Stereoselective Synthesis of α-Fluoro-α,β-unsaturated Esters from α-Fluoro-β-keto Esters via Deacylation
  作者：Wenbin Yi、Jinlong Qian、Meifang Lv、Chun Cai

  DOI：10.1055/s-0034-1378917

  日期：——

  The highly stereoselective olefination reaction of α-fluoro-β-keto esters for the synthesis of α-fluoro-α,β-unsaturated esters has been developed. The olefination combines nucleophilic addition, intramolecular nucleophilic addition, and elimination in one step, as well as provides a facile synthetic approach to α-fluoro-α,β-unsaturated esters which are important units in many biologically active compounds

  α-氟-β-酮酯的高度立体选择性烯化反应用于合成α-氟-α,β-不饱和酯已经被开发出来。烯化在一个步骤中结合了亲核加成、分子内亲核加成和消除，并为α-氟-α,β-不饱和酯提供了一种简便的合成方法，α-氟-α,β-不饱和酯是许多生物活性化合物中的重要单元和各种有用的前体功能组转换。