E-fluoro-2-cinnamate de methyle | 56695-79-5

• 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-fluoro-2-cinnamate de methyle
• 英文别名: methyl (E)-2-fluorocinnamate；(E)-methyl 2-fluoro-3-phenylacrylate；methyl (E)-2-fluoro-3-phenylprop-2-enoate
• CAS: 56695-79-5
• 化学式: C₁₀H₉FO₂
• 分子量: 180.179
• InChiKey: WXASNVQEFOHASF-VQHVLOKHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.1
• 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：

  E-fluoro-2-cinnamate de methyle 生成 (E)-2-fluoro-3-phenylprop-2-enoic acid
  参考文献：
  名称：

  Mechanistic and stereochemical study of phenylpyruvate tautomerase

  摘要：

  A variety of substrates and potential enol/enolate mimics for the product/transition state of the enzyme phenylpyruvate tautomerase (E.C. 5.3.2.1) have been prepared and studied. Their stereostructures have been secured by a combination of NMR spectroscopy based on vicinal H-F and H-C coupling constants and X-ray crystallography. On the basis of the inhibition by stereoisomeric substituted cinnamates, it has been concluded that the enzyme produces the thermodynamically less stable (E) enol via a syn tautomerization transition state. Free energy profiles for the reaction suggest that vinyl fluorides act as product analogues. Because amide and dicarboxylate enolate mimics are relatively poor inhibitors of the enzyme, it is believed that an enolate is not involved in the tautomerization process.

  DOI：

  10.1021/ja00069a006
• 作为产物：
  描述：

  (Z)-methyl 2-fluoro-3-phenylacrylate 以 乙腈 为溶剂， 反应 12.0h， 生成 E-fluoro-2-cinnamate de methyle
  参考文献：
  名称：

  Mechanistic and stereochemical study of phenylpyruvate tautomerase

  摘要：

  A variety of substrates and potential enol/enolate mimics for the product/transition state of the enzyme phenylpyruvate tautomerase (E.C. 5.3.2.1) have been prepared and studied. Their stereostructures have been secured by a combination of NMR spectroscopy based on vicinal H-F and H-C coupling constants and X-ray crystallography. On the basis of the inhibition by stereoisomeric substituted cinnamates, it has been concluded that the enzyme produces the thermodynamically less stable (E) enol via a syn tautomerization transition state. Free energy profiles for the reaction suggest that vinyl fluorides act as product analogues. Because amide and dicarboxylate enolate mimics are relatively poor inhibitors of the enzyme, it is believed that an enolate is not involved in the tautomerization process.

  DOI：

  10.1021/ja00069a006

文献信息

• Highly Efficient and Stereoselective Julia-Kocienski Protocol for the Synthesis of α-Fluoro-α,β-unsaturated Esters and Weinreb Amides Employing 3,5-Bis(trifluoromethyl)phenyl (BTFP) Sulfones
  作者：Diego A. Alonso、Mónica Fuensanta、Enrique Gómez-Bengoa、Carmen Nájera

  DOI：10.1002/adsc.200800194

  日期：2008.8.4

  α-Fluoroacetates 3 and Weinreb amide 4, bearing a α-[3,5-bis(trifluoromethyl)phenyl]sulfonyl (BTFP-sulfonyl) group at the α-position, are employed in the highly stereoselective synthesis of α-fluoro-α,β-unsaturated alkenoates and Weinreb amides, respectively. Aromatic and aliphatic aldehydes are condensed under extremely mild and simple reaction conditions using potassium carbonate in dimethylformamide

  α-氟-α的高度立体选择性合成中使用了在α位带有α-[3,5-双（三氟甲基）苯基]磺酰基（BTFP-磺酰基）基团的α-氟乙酸酯3和Weinreb酰胺4。 ，β-不饱和链烯酸酯和Weinreb酰胺。使用碳酸钾在二甲基甲酰胺中，在室温下，在固液相转移催化条件下，在极温和和简单的反应条件下，以高收率和高Z值缩合芳族和脂肪族醛-非对映选择性，特别是在氟化的Weinreb酰胺的情况下。一项详细的计算机理研究表明，最终应避免消除二氧化硫和3,5-双（三氟甲基）苯酚氧化物，并基于热力学和动力学方面的考虑，解释了该反应所观察到的高立体选择性。
• Organocatalyzed Sulfa-Michael Addition of Thiophenols on Trisubstituted α-Fluoroacrylates, a Straightforward Access to Chiral Fluorinated Compounds
  作者：Xin Huang、Emilie David、Philippe Jubault、Tatiana Besset、Samuel Couve-Bonnaire

  DOI：10.1021/acs.joc.0c02081

  日期：2020.11.6

  In this manuscript, a simple and efficient sulfa-Michael addition reaction of aryl thiols to trisubstituted α-fluoro-α,β-unsaturated esters both in racemic and, for the first time, in enantioselective version is reported. The commercially available dimer of cinchona derivatives (DHQ)2PYR was used as a catalyst. This strategy showed a great tolerance for various substrates and substituents, providing

  在该手稿中，报道了在外消旋体中以及首次以对映体选择性的方式，芳基硫醇与三取代的α-氟-α，β-不饱和酯的简单有效的磺胺-迈克尔加成反应。金鸡纳衍生物（DHQ）2 PYR的可商购二聚体用作催化剂。该策略显示出对各种底物和取代基的高度耐受性，提供了中等至优异的产率，中等至优异的非对映选择性（2：1至> 99：1）和低至良好的对映选择性（2至87％）。该反应已被用于合成地尔硫卓和噻替西姆这两种治疗剂的氟化类似物。
• 4-cyano-4-(fluorophenyl)-3-(substituted phenyl) butyric acids, esters and derivatives thereof, and a method of selectively controlling undesirable vegetation in rice therewith
  申请人：AMERICAN CYANAMID COMPANY

  公开号：EP0266725A1

  公开（公告）日：1988-05-11

  The invention relates to selective herbicidal 4-cyano-4-(fluorophenyl)-3-(substituted-phenyl)butyric acids, esters and derivatives thereof, and a method of selectively controlling undesirable vegetation in rice therewith.

  本发明涉及选择性除草的 4-氰基-4-(氟苯基)-3-(取代苯基)丁酸及其酯和衍生物，以及用其选择性控制水稻中不良植被的方法。
• Etemad-Moghadam, Guita; Seyden-Penne, Jacqueline, Bulletin de la Societe Chimique de France, 1985, # 3, p. 448 - 454
  作者：Etemad-Moghadam, Guita、Seyden-Penne, Jacqueline

  DOI：——

  日期：——
• ETEMAD-MOGHADAM, G.;SEYDEN-PENNE, J., BULL. SOC. CHIM. FR., 1985, N 3: COLLOQ. SCF 84, NANCY, SEPT., 1984. APPR+
  作者：ETEMAD-MOGHADAM, G.、SEYDEN-PENNE, J.

  DOI：——

  日期：——