(E)-diethyl 2-fluoro-3-ethyl fumarate | 135987-07-4

• 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: (E)-diethyl 2-fluoro-3-ethyl fumarate
• 英文别名: diethyl (Z)-2-ethyl-3-fluorobut-2-enedioate
• CAS: 135987-07-4
• 化学式: C₁₀H₁₅FO₄
• 分子量: 218.225
• InChiKey: CUPMNSLRTJVKJN-FPLPWBNLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  (E)-2-Fluoro-3-vinyl-but-2-enedioic acid diethyl ester 在 palladium on activated charcoal 氢气 作用下， 生成 (Z)-diethyl 2-fluoro-3-ethyl fumarate 、 (E)-diethyl 2-fluoro-3-ethyl fumarate
  参考文献：
  名称：

  A Novel Intramolecular Horner-Wadsworth-Emmons Reaction: A Simple and General Route to .alpha.-Fluoro-.alpha.,.beta.-unsaturated Diesters

  摘要：

  Diethyl (fluorocarbethoxymethyl)phosphonate (1), prepared from triethyl phosphite and ethyl bbromofluoroacetate, reacts with n-butyllithium in THF to give the phosphonate carbanion 2. Addition of the pregenerated carbanion 2 to a THF solution of methyl or ethyl oxalyl chloride at -78 degrees C forms the acylated phosphonate (EtO)(2)P(O)CF(COCO(2)R)CO(2)Et (3). In situ reaction of 3 with Grignard reagents affords alpha-fluoro-alpha,beta-unsaturated diesters R'(CO(2)R)C=CFCO(2)Et in moderate to good yields with high E-stereoselectivity. The reaction is applicable to primary, secondary, and tertiary alkyl, alkenyl, alkynyl, aryl, cyclohexyl, and perfluorinated Grignard reagents. The assignment of E and Z configuration is based on NOE experiment. The E/Z ratio of unsaturated diesters formed in the reaction varies with the metal ion and cosolvent. However, solvents and bases have little influence on the stereoselectivity.

  DOI：

  10.1021/jo00102a038

文献信息

• Ethyl phenylsulfinyl fluoroacetate, a new and versatile reagent for the preparation of α-fluoro-α,β-unsaturated carboxylic acid esters
  作者：Thomas Allmendinger

  DOI：10.1016/s0040-4020(01)80956-x

  日期：1991.1

  The title compound 2 can be alkylated with a wide range of alkyl halides and Michael acceptors. Subsequent thermal elimination of phenyl sulfinic acid 3 leads to α-fluoro-α,β-unsaturated ethyl carboxylates 5 and 10, an important class of intermediates for fluorine containing biologically active compounds.

  标题化合物2可以用多种烷基卤化物和迈克尔受体烷基化。随后热消除苯基亚磺酸3会导致α-氟代-α，β-不饱和羧酸乙酯5和10，这是含氟生物活性化合物的重要中间体。
• Isolation and Characterization of intermediate in the Synthesis of α-Fluorodiesters
  作者：Hou-Jen Tsai

  DOI：10.1002/jccs.199800082

  日期：1998.8

  AbstractThe anion [(EtO)2P(O)CFCO2Et]−Li+, pregenerated from its precursor diethyl (carboethoxyfluoromethyl)phosphonate (EtO)2P(O)CFHCO2Et and n‐butyllithium, was added via syringe to a THF solution of ethyl oxaiyl chloride to yield an acylated phosphonate (EtO)2P(O)CF(COCO2Et)CO2Et. In situ reaction with Grignard reagents RMgX produces the α‐fluorodiesters (E,Z)‐R(CO2Et)C=CFCO2Et in good yields. In contrast, addition of ethyl oxalyl chloride to a THF solution of diethyl (carboethoxyfluoromethyl)phosphonate anion gives an isolated intermediate (EtO)2P(O)CFCO2Et(CO2Et)C=CFCO2Et. Subsequent reaction of this isolated intermediate with Grignard reagents also affords a one‐pot synthesis of the α‐fluorodiesters with high E‐stereoselectivity. The E‐stereoselectivity increases when HMPT or DMPU is used as a cosolvent in the preparation of diethyl 2‐fluoro‐3‐phenylfumarate (E,Z)‐Ph(CO2Et)C=CFCO2Et.
• A Novel Intramolecular Horner-Wadsworth-Emmons Reaction: A Simple and General Route to .alpha.-Fluoro-.alpha.,.beta.-unsaturated Diesters
  作者：Hou-Jen Tsai、Alagappan Thenappan、Donald J. Burton

  DOI：10.1021/jo00102a038

  日期：1994.11

  Diethyl (fluorocarbethoxymethyl)phosphonate (1), prepared from triethyl phosphite and ethyl bbromofluoroacetate, reacts with n-butyllithium in THF to give the phosphonate carbanion 2. Addition of the pregenerated carbanion 2 to a THF solution of methyl or ethyl oxalyl chloride at -78 degrees C forms the acylated phosphonate (EtO)(2)P(O)CF(COCO(2)R)CO(2)Et (3). In situ reaction of 3 with Grignard reagents affords alpha-fluoro-alpha,beta-unsaturated diesters R'(CO(2)R)C=CFCO(2)Et in moderate to good yields with high E-stereoselectivity. The reaction is applicable to primary, secondary, and tertiary alkyl, alkenyl, alkynyl, aryl, cyclohexyl, and perfluorinated Grignard reagents. The assignment of E and Z configuration is based on NOE experiment. The E/Z ratio of unsaturated diesters formed in the reaction varies with the metal ion and cosolvent. However, solvents and bases have little influence on the stereoselectivity.