ethyl (E)-4,4-difluoro-3-(p-methoxyphenyl)pent-2-enoate | 144464-71-1

• 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)-4,4-difluoro-3-(p-methoxyphenyl)pent-2-enoate
• CAS: 144464-71-1
• 化学式: C₁₄H₁₆F₂O₃
• 分子量: 270.276
• InChiKey: TXTOLMSMERDVML-FMIVXFBMSA-N

物化性质

• 沸点：
  363.1±42.0 °C(Predicted)
• 密度：
  1.134±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  19.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  ethyl (E)-4,4-difluoro-3-(p-methoxyphenyl)pent-2-enoate 在 palladium on activated charcoal 韦德伊斯试剂 、 氢气 、 lithium diisopropyl amide 作用下， 以 乙醇 为溶剂， 反应 45.0h， 生成 threo ethyl 4,4-difluoro-2-hydroxy-3-(p-methoxyphenyl)pentanoate
  参考文献：
  名称：

  Synthesis of DL-threo-3-(1-fluoro-1-methylethyl)- and DL-threo-3-(1,1-difluoroethyl)malic acids. Mechanistic studies of 3-isopropylmalate dehydrogenase

  摘要：

  For both mechanistic studies and the development of novel inhibitors of 3-isopropylmalate dehydrogenase enzyme (IPMDH), which is involved in the rate-determining step in the biosynthetic pathway of the essential amino acid L-leucine, (2R*,3S*)-3-(1-fluoro-1-methylethyl)- and (2R*,3S*)-3-(1,1-difluoroethyl)malic acids (F-IPM and F-2-EM) were designed based on the concept of mechanism-based inhibition, and the reaction kinetics with these fluorinated substrates were analysed, The reaction of F-IPM with IPMDH was studied by NMR spectroscopy and product isolation. F-IPM underwent, after the normal enzyme reaction, the expected additional elimination reaction to afford an alpha,beta-unsaturated carbonyl product, which turned out not to participate in any covalent-bond-forming reaction. The conformation of the reaction intermediate during the IPMDH reaction and the functional-group arrangement in the active site of IPMDH are discussed.

  DOI：

  10.1039/p19950001905
• 作为产物：
  描述：

  4-溴苯甲醚 在 叔丁基锂 作用下， 以 甲苯 为溶剂， 反应 24.25h， 生成 ethyl (E)-4,4-difluoro-3-(p-methoxyphenyl)pent-2-enoate
  参考文献：
  名称：

  Synthesis of DL-threo-3-(1-fluoro-1-methylethyl)- and DL-threo-3-(1,1-difluoroethyl)malic acids. Mechanistic studies of 3-isopropylmalate dehydrogenase

  摘要：

  For both mechanistic studies and the development of novel inhibitors of 3-isopropylmalate dehydrogenase enzyme (IPMDH), which is involved in the rate-determining step in the biosynthetic pathway of the essential amino acid L-leucine, (2R*,3S*)-3-(1-fluoro-1-methylethyl)- and (2R*,3S*)-3-(1,1-difluoroethyl)malic acids (F-IPM and F-2-EM) were designed based on the concept of mechanism-based inhibition, and the reaction kinetics with these fluorinated substrates were analysed, The reaction of F-IPM with IPMDH was studied by NMR spectroscopy and product isolation. F-IPM underwent, after the normal enzyme reaction, the expected additional elimination reaction to afford an alpha,beta-unsaturated carbonyl product, which turned out not to participate in any covalent-bond-forming reaction. The conformation of the reaction intermediate during the IPMDH reaction and the functional-group arrangement in the active site of IPMDH are discussed.

  DOI：

  10.1039/p19950001905

文献信息

• Remarkable reversal of stereoselectivity in Wittig-type olefinations of α-fluorinated alkyl aryl ketones
  作者：Tadashi Eguchi、Tetsuya Aoyama、Katsumi Kakinuma

  DOI：10.1016/s0040-4039(00)61141-3

  日期：1992.9

  reversal of stereoselectivity in the Wittig-type olefinations of α-fluorinated alkyl aryl ketones were described. Stabilized Wittig and Horner-Emmons reagents with these ketones selectively afforded the olefinic products in the stereochemically oppposite fashion to the non-flourinated ketone cases. The Still's reagent further reversed the stereochemical outcome with the fluorinated ketones.

  描述了在α-氟化烷基芳基酮的维蒂希型烯化反应中显着的反应性和立体选择性的逆转。具有这些酮的稳定化的Wittig和Horner-Emmons试剂选择性地提供了与非氟化酮盒立体化学相反的烯烃产物。斯蒂尔试剂与氟化酮进一步逆转了立体化学结果。