ethyl 2-fluoro-4-methyl-3-oxo-pentanoate | 127224-01-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: ethyl 2-fluoro-4-methyl-3-oxo-pentanoate
• 英文别名: Ethyl 2-fluoro-4-methyl-3-oxopentanoate
• CAS: 127224-01-5
• 化学式: C₈H₁₃FO₃
• 分子量: 176.188
• InChiKey: CMNJNHWHNXWRRC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 2-fluoro-4-methyl-3-oxo-pentanoate 在 三氟乙酸 、 N,N-diisopropyldibenzo[d,f][1,3,2]dioxaphosphepin-6-amine 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 二氯甲烷 为溶剂， 反应 19.67h， 生成 ethyl 3-fluoro-5-methylidene-2-(propan-2-yl)-3,4,5,6-tetrahydropyridine-3-carboxylate
  参考文献：
  名称：

  氟化N-杂环的Pd催化[4 + 2]环化方法

  摘要：

  3-氟和三氟甲硫基哌啶是发现化学的重要组成部分。我们报告了一种简单有效的方法，可访问具有丰富功能的这些化合物的类似物，从而可以通过非对映异构体的高度化学控制对其进行化学选择性衍生化。

  DOI：

  10.1021/acs.orglett.1c00752
• 作为产物：
  描述：

  异丁酰乙酸乙酯 在 N-fluorobis<(trifluoromethyl)sulfonyl>imide 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 14.0h， 以91%的产率得到ethyl 2-fluoro-4-methyl-3-oxo-pentanoate
  参考文献：
  名称：

  N-fluoro perfluoroalkylsulphonimides: efficient reagents for the fluorination of 1,3-dicarbonyl derivatives

  摘要：

  1,3-二羰基衍生物与氟磺酰亚胺的氟化反应可以高产率地生成2-氟或2,2-二氟产物。

  DOI：

  10.1039/c39910000179

文献信息

• N-fluoro perfluoroalkylsulphonimides: efficient reagents for the fluorination of 1,3-dicarbonyl derivatives
  作者：Ze-Qi Xu、Darryl D. DesMarteau、Yoshihiko Gotoh

  DOI：10.1039/c39910000179

  日期：——

  Fluorination of 1,3-dicarbonyl derivatives with N-fluoro sulphonimides afforded either 2-fluoro or 2,2-difluoro products in high yields.

  1,3-二羰基衍生物与氟磺酰亚胺的氟化反应可以高产率地生成2-氟或2,2-二氟产物。
• Electrocatalytic Allylic C−H Alkylation Enabled by a Dual‐Function Cobalt Catalyst**
  作者：Ming Chen、Zheng‐Jian Wu、Jinshuai Song、Hai‐Chao Xu

  DOI：10.1002/anie.202115954

  日期：2022.3.28

  An electrocatalytic allylic C−H alkylation reaction with carbon nucleophiles is reported, which employs an easily available cobalt–salen complex as the molecular catalyst. The method is characterized by its excellent functional group tolerance, substrate compatibility with both linear and branched terminal alkenes, and scalability (up to 200 mmol scale) with a low loading of electrolyte (down to 0

  报道了与碳亲核试剂的电催化烯丙基 C-H 烷基化反应，该反应使用易于获得的钴-salen 配合物作为分子催化剂。该方法的特点是其优异的官能团耐受性、与直链和支链末端烯烃的底物相容性以及可扩展性（高达 200 mmol 规模）和低电解质负载量（低至 0.05 equiv）。
• Acylation of fluorocarbethoxy-substituted ylides: a simple and general route to .alpha.-fluoro .beta.-keto esters
  作者：Alagappan Thenappan、Donald J. Burton

  DOI：10.1021/jo00001a052

  日期：1991.1

  (Fluorocarbethoxymethylene)tri-n-butylphosphorane (3) reacts with acid chlorides and anhydrides to form the corresponding carbon acylated phosphonium salts 4, and hydrolysis of 4 under mild basic conditions provides RCOCFHCOOEt (8) in moderate yields. The reaction is applicable to primary, secondary, tertiary, cyclic, aromatic, and ester-substituted acid chlorides. Acylation with ethyl chloroformate and ethyl chlorothioformate leads to the diesters CFH(COOEt)2 and EtSCOCFHCOOEt. Extension of this reaction sequence to perfluorinated and partially fluorinated acid chlorides did not proceed cleanly to give the expected phosphonium salts. However, the anion derived from (EtO)2P(O)CFHC(O)OEt reacts with R(F)COCl to form the corresponding C-acylated phosphonates 10, and hydrolysis of 10 gives R(F)COCFHCOOEt.
• Selective, Electrophilic Fluorinations Using N-Fluoro-o-benzenedisulfonimide
  作者：Franklin A. Davis、Wei Han、Christopher K. Murphy

  DOI：10.1021/jo00120a014

  日期：1995.7

  The synthesis of N-fluoro-o-benzenedisulfonimide (NFOBS, 2) and its use as an ''electrophilic'' fluorinating reagent with nucleophilic substrates is described and compared with that of N-fluorobenzenesulfonimide (NFSi, 3). NFOBS (2) is prepared in three steps in 81% overall yield from commercially available o-benzenedisulfonic acid (4) and involves treatment of o-benzenedisulfonimide (6) with dilute fluorine (10% F-2/N-2). Reaction of 2 with metal enolates, silyl enol ethers, and 1,3-dicarbonyl compounds affords the corresponding alpha-fluoro compounds in yields up to 95%, with good control of mono- and difluorination. Fluorination of ortho-metalated aromatic compounds was achieved in modest to good yields (10-80%). While the reactivities of 2 and 3 are similar, better yields were observed with the former reagent in the fluorination of metal enolates, Grignard and lithium reagents, while 3 gave better results with the ortho-lithiated aromatic substrates. The available evidence suggests an S(N)2-type mechanism for the fluorination of nucleophilic substrates by these reagents.
• An expedient synthesis of α-fluoro-β-ketoesters
  作者：Alagappan Thenappan、Donald J. Burton

  DOI：10.1016/s0040-4039(01)93318-0

  日期：——