ethyl 3,3-difluoro-4-phenyl-2-oxo-5-hexenoate | 168101-93-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl 3,3-difluoro-4-phenyl-2-oxo-5-hexenoate
• 英文别名: Ethyl 3,3-difluoro-2-oxo-4-phenylhex-5-enoate
• CAS: 168101-93-7
• 化学式: C₁₄H₁₄F₂O₃
• 分子量: 268.26
• InChiKey: OUOWQJCBBJXNOX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl 3,3-difluoro-4-phenyl-2-oxo-5-hexenoate 在 rhodium(II) acetate dimer 盐酸 、 N,N-二异丙基乙胺 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 (1S,3R,4S)-2,2-Difluoro-3-phenyl-bicyclo[2.1.0]pentane-1-carboxylic acid ethyl ester
  参考文献：
  名称：

  铑催化的δ，α-不饱和ββ-二氟-α-重氮酯的分解，通过分子内环丙烷化直接形成双环[2.1.0]戊烷环系统

  摘要：

  由相应的α-酮基酯制备的几种δ，μ-不饱和β，β-二氟-α-重氮酯经历铑催化的分子内环丙烷化反应，从而导致双环[2.1.0]戊烷环系统的空前形成。

  DOI：

  10.1039/p19960002337
• 作为产物：
  描述：

  3,3-Difluoro-2-((E)-3-phenyl-allyloxy)-acrylic acid ethyl ester 以 苯 为溶剂， 反应 1.0h， 生成 ethyl 3,3-difluoro-4-phenyl-2-oxo-5-hexenoate
  参考文献：
  名称：

  .delta.,.epsilon.-Unsaturated .beta.,.beta.-Difluoro-.alpha.-keto Esters: Novel Synthesis and Utility as Precursors of .beta.,.beta.-Difluoro-.alpha.-amino Acids

  摘要：

  Treatment of the hemiketals 6 formed from ethyl trifluoropyruvate and primary allylic alcohols with SOCl2 and pyridine readily afforded a number of alpha-chloro-beta,beta,beta-trifluorolactyl allyl ethers 2. Subsequent reductive dechlorofluorination from 2 led to the formation of allyl-substituted difluoroenol pyruvyl ethers 3 whose Claisen rearrangement provided a convenient access to a variety of delta,epsilon-unsaturated beta,beta-difluoro-alpha-keto esters 4. As further transformation, direct conversion of beta,beta-difluoro-alpha-keto esters to the corresponding beta,beta-difluoro-alpha-amino acids was achieved by reductive amination of the corresponding alpha-keto acids with NH3 . H2O/NaBH4. Furthermore, use of the prepared beta beta-difluoro-alpha-keto ester 4a as a common precursor of other structurally related beta,beta-difluoro-alpha-amino acids was demonstrated by the synthesis of beta,beta-difluoroproline (18) and beta,beta-difluoroglutamic acid (23) through synthetic elaboration of its inherent double bond.

  DOI：

  10.1021/jo00125a013

文献信息

• Rhodium-catalysed decomposition of δ,ε-unsaturated ββ-difluoro-α-diazo esters, the direct formation of bicyclo[2.1.0]pentane ring systems via intramolecular cyclopropanation
  作者：Guo-qiang Shi、Wei-ling Cai

  DOI：10.1039/p19960002337

  日期：——

  Several δ,ε-unsaturated β,β-difluoro-α-diazo esters, prepared from the corresponding α-keto esters, undergo rhodium-catalysed intramolecular cyclopropanation reaction leading to the unprecedented formation of bicyclo[2.1.0]pentane ring systems.

  由相应的α-酮基酯制备的几种δ，μ-不饱和β，β-二氟-α-重氮酯经历铑催化的分子内环丙烷化反应，从而导致双环[2.1.0]戊烷环系统的空前形成。
• .delta.,.epsilon.-Unsaturated .beta.,.beta.-Difluoro-.alpha.-keto Esters: Novel Synthesis and Utility as Precursors of .beta.,.beta.-Difluoro-.alpha.-amino Acids
  作者：Guo-qiang Shi、Wei-ling Cai

  DOI：10.1021/jo00125a013

  日期：1995.10

  Treatment of the hemiketals 6 formed from ethyl trifluoropyruvate and primary allylic alcohols with SOCl2 and pyridine readily afforded a number of alpha-chloro-beta,beta,beta-trifluorolactyl allyl ethers 2. Subsequent reductive dechlorofluorination from 2 led to the formation of allyl-substituted difluoroenol pyruvyl ethers 3 whose Claisen rearrangement provided a convenient access to a variety of delta,epsilon-unsaturated beta,beta-difluoro-alpha-keto esters 4. As further transformation, direct conversion of beta,beta-difluoro-alpha-keto esters to the corresponding beta,beta-difluoro-alpha-amino acids was achieved by reductive amination of the corresponding alpha-keto acids with NH3 . H2O/NaBH4. Furthermore, use of the prepared beta beta-difluoro-alpha-keto ester 4a as a common precursor of other structurally related beta,beta-difluoro-alpha-amino acids was demonstrated by the synthesis of beta,beta-difluoroproline (18) and beta,beta-difluoroglutamic acid (23) through synthetic elaboration of its inherent double bond.