(Z)-2-Fluoro-3-vinyl-but-2-enedioic acid 1-ethyl ester 4-methyl ester | 145343-55-1

• 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: (Z)-2-Fluoro-3-vinyl-but-2-enedioic acid 1-ethyl ester 4-methyl ester
• CAS: 145343-55-1
• 化学式: C₉H₁₁FO₄
• 分子量: 202.182
• InChiKey: LBSTZIMNYOSZTR-SREVYHEPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.13
• 重原子数：
  14.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  乙烯基溴化镁 、 2-(Diethoxy-phosphoryl)-2-fluoro-3-oxo-succinic acid 1-ethyl ester 4-methyl ester 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 生成 (E)-2-Fluoro-3-vinyl-but-2-enedioic acid 1-ethyl ester 4-methyl ester 、 (Z)-2-Fluoro-3-vinyl-but-2-enedioic acid 1-ethyl ester 4-methyl ester
  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

• STEREOSELECTIVE SYNTHESIS OF MONOFLUORO-OLEFINS FROM DIISOPROPYL (CARBOETHOXYFLUORO-METHYL)PHOSPHONATE
  作者：Hou-Jen Tsai、Shyi-Chen Wu

  DOI：10.1080/10426500008042107

  日期：2000.6.1

  Treatment of ethyl oxalyl chloride or methyl oxalyl chloride with lithium diisopropyl(carboethoxyfluoromethyl)phosphonate [(i-PrO)(2)P(O)CFCO2Et]Li--(+) 2 followed by in situ nucleophilic addition with methylmagnesium iodide or vinyl magnesium bromide affords with exclusive E-stereoselectivity formation of diethyl-2-fluoro-3-methyl fumarate (CH3)(CO2Et)C=CFCO2Et 4 or 75% of the E-isomer of alpha-fluoro-beta-vinyl-alpha,beta-unsaturated diester (E,Z)-(CH2=CH)(CO2C2H5)C=CFCO2Et 5, respectively. However, direct reaction of ethyl pyruvate with 2 gives the fluoro-olefin (CH3)(CO2Et)C=CFCO2Et 4 with 79% E-stereoselectivity. The E/Z ratio of (CH2=CH)(CO2Et)C=CFCO2Et 5 depends on the HMPT or DMPU cosolvents present in the reaction mixture.
• An expedient synthesis of α-fluoro-α,β-unsaturated diesters
  作者：Hou-Jen Tsai、Alagappan Thenappan、Donald J. Burton

  DOI：10.1016/s0040-4039(00)60990-5

  日期：1992.10

  Acylation of [(EtO)2P(O)CFCO2Et]-Li+ (2) with alkyloxalyl chlorides followed by subsequent reaction of the acylated phosphonates with Grignard reagents provides the title compounds in moderate to good yields with high E-stereoselectivity.