ethyl 2,2-difluoro-3-hydroxybutanoate | 321942-91-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: ethyl 2,2-difluoro-3-hydroxybutanoate
• CAS: 321942-91-0
• 化学式: C₆H₁₀F₂O₃
• mdl: MFCD00720836
• 分子量: 168.14
• InChiKey: ONGVAFSENCMVGI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.833
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl 2,2-difluoro-3-hydroxybutanoate 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 以73%的产率得到2,2-二氟乙酰乙酸乙酯
  参考文献：
  名称：

  Chemoenzymatic synthesis of optically active alcohol and β-amino-acid derivative containing the difluoromethylene group

  摘要：

  The bioreduction of alpha,alpha-difluorinated ketones, ethyl 2,2-difluoro-3-oxobutanoate (2a) and 2,2-difluoro-1-phenyl-1,3-butanedione (2b), with cells of recombinant Escherichia coli overproducing SCR (Saccharomyces cerevisiae carbonyl reductase from bakers' yeast) and GDH (glucose dehydrogenase from Bacillus megaterium) gave enantiomerically pure alcohols, ethyl (S)-2,2-difluoro-3-hydroxybutanoate ((S)-1a) and (S)-2,2-difluoro-3-hydroxy-1-phenyl-1-butanone ((S)-1b), respectively, in the presence of NADP(+) and glucose in buffer. The reductions of 2a and 2b proceeded completely at the substrate concentrations of 0.4 M (67 g/L) and 1.0 M (200 g/L), respectively. The opposite enantiomers (R)-1a and (R)-1b were also produced by enzyme E039 (a mixture of carbonyl reductase and formate dehydrogenase) contained in Chiralscreen OH (Daicel Chemical Industries) in the presence of NADH and sodium formate in buffer. Enantiomerically pure (S)-1a was converted by organic synthetic methods into an a,a-difluorinated derivative of (R)-beta-aminobutyric acid (BABA) in three steps. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2010.05.009
• 作为产物：
  描述：

  二氟溴乙酸乙酯 、 乙醛 在 锌 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以43%的产率得到ethyl 2,2-difluoro-3-hydroxybutanoate
  参考文献：
  名称：

  Chemoenzymatic synthesis of optically active alcohol and β-amino-acid derivative containing the difluoromethylene group

  摘要：

  The bioreduction of alpha,alpha-difluorinated ketones, ethyl 2,2-difluoro-3-oxobutanoate (2a) and 2,2-difluoro-1-phenyl-1,3-butanedione (2b), with cells of recombinant Escherichia coli overproducing SCR (Saccharomyces cerevisiae carbonyl reductase from bakers' yeast) and GDH (glucose dehydrogenase from Bacillus megaterium) gave enantiomerically pure alcohols, ethyl (S)-2,2-difluoro-3-hydroxybutanoate ((S)-1a) and (S)-2,2-difluoro-3-hydroxy-1-phenyl-1-butanone ((S)-1b), respectively, in the presence of NADP(+) and glucose in buffer. The reductions of 2a and 2b proceeded completely at the substrate concentrations of 0.4 M (67 g/L) and 1.0 M (200 g/L), respectively. The opposite enantiomers (R)-1a and (R)-1b were also produced by enzyme E039 (a mixture of carbonyl reductase and formate dehydrogenase) contained in Chiralscreen OH (Daicel Chemical Industries) in the presence of NADH and sodium formate in buffer. Enantiomerically pure (S)-1a was converted by organic synthetic methods into an a,a-difluorinated derivative of (R)-beta-aminobutyric acid (BABA) in three steps. (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcatb.2010.05.009

文献信息

• Synthesis of stereocontrolled α,α-difluoro-β-hydroxycarbonyl materials
  作者：Takeshi Kaneda、Shinya Komura、Tomoya Kitazume

  DOI：10.1016/j.jfluchem.2004.09.026

  日期：2005.1

  Synthesis and synthetic utilities of stereocontrolled alpha, alpha-di fluoro-beta-hydroxy-gamma,delta-unsaturated carbonyl compounds via enzymatic resolution with lipase PS (Pseudomonas cepacia, Amano Pharmaceutical Co. Ltd.) or lipase MY (Candida rugosa, Meito Sangyo Co. Ltd.) were described, and then the absolute configuration of obtained chiral materials was determined by the modified Mosher's method. (C) 2004 Elsevier B.V. All rights reserved.
• Cyclization reactions of β,β-difluoroalkyl radicals (-CF2-C·) for synthesizing gem-difluorocyclic compounds
  作者：Tsutomu Morikawa、Yoshitoshi Kodama、Jun Uchida、Masami Takano、Yoshiaki Washio、Takeo Taguchi

  DOI：10.1016/s0040-4020(01)81990-6

  日期：1992.1

  Cyclization reactions of beta,beta-difluoroalkyl radicals were carried out. 5 or 6-Exo selective radical cyclizations gave gem-difluorocyclopentane or -cyclohexane derivatives in 53 - 96% yields. 2,5-Disubstituted-3,3-difluorotetrahydropyran derivatives were prepared in 36 - 82% yields with moderate trans-selectivity (2.0 : 1-3.1 : 1). 4,5-Disubstituted-3,3-difluorotetrahydopyran derivatives were obtained via radical deoxygenation in 60 - 74% yields. High stereo-selectivity of radical cyclization for the formation of gem-fluorotetrahydropyran rings was achieved by introducing the bulky TBDPS group onto the acceptor double bond.
• Chemoenzymatic synthesis of optically active alcohol and β-amino-acid derivative containing the difluoromethylene group
  作者：Tadashi Ema、Taro Kadoya、Kumiko Akihara、Takashi Sakai

  DOI：10.1016/j.molcatb.2010.05.009

  日期：2010.9

  The bioreduction of alpha,alpha-difluorinated ketones, ethyl 2,2-difluoro-3-oxobutanoate (2a) and 2,2-difluoro-1-phenyl-1,3-butanedione (2b), with cells of recombinant Escherichia coli overproducing SCR (Saccharomyces cerevisiae carbonyl reductase from bakers' yeast) and GDH (glucose dehydrogenase from Bacillus megaterium) gave enantiomerically pure alcohols, ethyl (S)-2,2-difluoro-3-hydroxybutanoate ((S)-1a) and (S)-2,2-difluoro-3-hydroxy-1-phenyl-1-butanone ((S)-1b), respectively, in the presence of NADP(+) and glucose in buffer. The reductions of 2a and 2b proceeded completely at the substrate concentrations of 0.4 M (67 g/L) and 1.0 M (200 g/L), respectively. The opposite enantiomers (R)-1a and (R)-1b were also produced by enzyme E039 (a mixture of carbonyl reductase and formate dehydrogenase) contained in Chiralscreen OH (Daicel Chemical Industries) in the presence of NADH and sodium formate in buffer. Enantiomerically pure (S)-1a was converted by organic synthetic methods into an a,a-difluorinated derivative of (R)-beta-aminobutyric acid (BABA) in three steps. (C) 2010 Elsevier B.V. All rights reserved.