ethyl 3-phenyl-4,4-difluoro-3-butenoate | 852561-60-5

• 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-phenyl-4,4-difluoro-3-butenoate
• 英文别名: ethyl 4,4-difluoro-3-phenyl-3-butenoate；ethyl 4,4-difluoro-3-phenylbut-3-enoate
• CAS: 852561-60-5
• 化学式: C₁₂H₁₂F₂O₂
• 分子量: 226.223
• InChiKey: HARCWOHLJPTPPH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  ethyl 3-phenyl-4,4-difluoro-3-butenoate 在 palladium on activated charcoal phosphate buffer 、 Novozym 435 、 氢气 作用下， 以 甲醇 为溶剂， 20.0 ℃ 、490.0 kPa 条件下， 反应 3.0h， 生成 (S)-4,4-difluoro-3-phenylbutanoic acid
  参考文献：
  名称：

  Stereocontrolled Synthesis of β-Difluoromethylated Materials

  摘要：

  Investigation of synthetic routes for regio- and stereocontrolled fluorinated materials with a difluoromethyl group, using ethyl bromodifluoroacetate as a starting material, is described. In particular, (E)-difluoromethylated trisubstituted olefins were prepared via the proton migration reaction catalyzed by using fluoride anion. Further, optically active beta-difluoromethyl esters were obtained by the enzymatic resolution.

  DOI：

  10.1021/jo050634u
• 作为产物：
  描述：

  2-溴-2,2-二氟-1-苯乙酮 在 sodium hydride 、 锌 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 7.0h， 生成 ethyl 3-phenyl-4,4-difluoro-3-butenoate
  参考文献：
  名称：

  Stereocontrolled Synthesis of β-Difluoromethylated Materials

  摘要：

  Investigation of synthetic routes for regio- and stereocontrolled fluorinated materials with a difluoromethyl group, using ethyl bromodifluoroacetate as a starting material, is described. In particular, (E)-difluoromethylated trisubstituted olefins were prepared via the proton migration reaction catalyzed by using fluoride anion. Further, optically active beta-difluoromethyl esters were obtained by the enzymatic resolution.

  DOI：

  10.1021/jo050634u

文献信息

• Umpolung Difunctionalization of Carbonyls via Visible-Light Photoredox Catalytic Radical-Carbanion Relay
  作者：Shun Wang、Bei-Yi Cheng、Matea Sršen、Burkhard König

  DOI：10.1021/jacs.0c00629

  日期：2020.4.22

  catalysis with the Wolff–Kishner (WK) reaction allows the difunctionalization of carbonyl groups by a radical-carbanion relay sequence (photo-Wolff–Kishner reaction). Photoredox initiated radical addition to N-sulfonylhydrazones yields α-functionalized carbanions following the WK-type mechanism. With sulfur-centered radicals, the carbanions are further functionalized by reaction with electrophiles

  光氧化还原催化与沃尔夫-基什纳 (WK) 反应相结合，可以通过自由基-碳负离子中继序列（光沃尔夫-基什纳反应）对羰基进行双官能化。光氧化还原引发自由基加成至 N-磺酰腙，按照 WK 型机制产生 α-功能化碳负离子。对于以硫为中心的自由基，碳负离子通过与包括 CO2 和醛在内的亲电子试剂反应而进一步官能化，而 CF3 自由基加成则通过生成的 α-CF3 碳负离子的 β-氟化物消除提供了多种偕二氟烯烃。 80 多个底物示例证明了该反应序列的广泛适用性。包括自由基抑制、氘标记、荧光猝灭、循环伏安法和控制实验在内的一系列研究支持了所提出的自由基-碳负离子中继机制。
• An efficient method for the synthesis of gem-difluoroolefins
  作者：Chun-Ru Cao、Song Ou、Min Jiang、Jin-Tao Liu

  DOI：10.1016/j.tetlet.2016.12.070

  日期：2017.2

  A series of gem-difluoroolefin derivatives were synthesized in moderate to good yields by the reaction of α,α-difluoro-β-carbonyl benzothiazol-2-yl sulfones (DFBTs) with various carbon nucleophiles. Using dl-proline as organocatalyst, the reaction of DFBT with acetone gave a tertiary alcohol, which could be further converted to the corresponding difluoroolefin by LDA.

  通过α，α-二氟-β-羰基苯并噻唑-2-基砜（DFBT）与各种碳亲核试剂的反应，以中等至良好的产率合成了一系列宝石-二氟烯烃衍生物。使用dl-脯氨酸作为有机催化剂，DFBT与丙酮的反应产生了叔醇，其可以通过LDA进一步转化为相应的二氟烯烃。
• Nickel-catalyzed asymmetric transfer hydrogenation of conjugated olefins
  作者：Siyu Guo、Peng Yang、Jianrong (Steve) Zhou

  DOI：10.1039/c5cc01632k

  日期：——

  Asymmetric transfer hydrogenation of electron-deficient olefins is realized with nickel catalysts supported by strongly [sigma]-donating bisphosphines. Deuterium labeling experiments points to a reaction sequence of formate decarboxylation, asymmetric hydride insertion...

  缺电子的烯烃的不对称转移氢化是由强σ供体双膦负载的镍催化剂实现的。氘标记实验指出甲酸脱羧，不对称氢化物插入的反应顺序...
• An efficient stereoselective synthesis of difluoromethylated alkenes in a microreactor
  作者：Tomoya Kitazume、Kouichi Kawai、Takashi Nihei、Noriaki Miyake

  DOI：10.1016/j.jfluchem.2004.10.008

  日期：2005.1

  Synthetic utility of microreactors and highly stereoselective isomerization (>99:<1) of terminal difluoromethylated alkenes to (E)-difluoromethylated alkenes with TBAF in DMF, are described. (C) 2004 Elsevier B.V. All rights reserved.
• 10.1039/d4cc00918e
  作者：Yang, Peng、Yu, Haiping、Zhai, Runze、Zhou, Jianrong Steve、Tang, Bo

  DOI：10.1039/d4cc00918e

  日期：——