(E)-diethyl 2-fluoro-3-methyl fumarate | 145343-48-2

• 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-methyl fumarate
• 英文别名: diethyl (E)-2-fluoro-3-methylbut-2-enedioate
• CAS: 145343-48-2
• 化学式: C₉H₁₃FO₄
• 分子量: 204.198
• InChiKey: REMDXJPZTJQKQB-VOTSOKGWSA-N

物化性质

• 沸点：
  247.9±30.0 °C(Predicted)
• 密度：
  1.117±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (E)-diethyl 2-fluoro-3-methyl fumarate 在 C₃₇H₄₁IrN₂PS⁽¹⁺⁾*C₃₂H₁₂BF₂₄^(1-) 、 氢气 作用下， 以 甲苯 为溶剂， 20.0 ℃ 、10.0 MPa 条件下， 反应 24.0h， 以19%的产率得到diethyl 2-fluoro-3-methylsuccinate
  参考文献：
  名称：

  具有两个连续立体中心的氟基团的非对映选择性和对映选择性合成

  摘要：

  手性氟的合成，特别是具有两个连续立体中心的手性氟分子，由于其制备方法的数量有限，引起了人们对研究的极大兴趣。在此，我们报告了通过氮杂双环铱-恶唑啉-膦催化氢化容易获得的氟乙烯，以原子经济和高度立体选择性合成具有两个连续立体中心的手性氟分子。发现具有各种官能团的各种芳香族、脂肪族和杂环系统与反应相容，并提供非常理想的产物，作为具有优异对映选择性的单一非对映异构体。

  DOI：

  10.1021/jacs.8b08778
• 作为产物：
  描述：

  三乙基2-膦酰基丙酯 在 9-噻吨酮 、 lithium perchlorate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 反应 3.25h， 生成 (E)-diethyl 2-fluoro-3-methyl fumarate
  参考文献：
  名称：

  通过选择性能量转移催化利用烯烃异构化中的 n→π* 相互作用

  摘要：

  研究了富马酸到马来酸 ( E → Z ) 异构化，以验证 n O → π C=O * 相互作用作为反热力学异构化的驱动力。采用廉价的噻吨酮作为敏化剂，开发了基于选择性能量转移催化的通用方案，用于转化各种富马酸酯衍生物，包括四取代烯烃。 X 射线晶体学证实了 n O →π C=O * 相互作用的参与。

  DOI：

  10.1002/anie.202113600

文献信息

• Synthesis of phenyl substituted fluoro-olefins
  作者：Hou-Jen Tsai

  DOI：10.1016/0040-4039(95)02218-x

  日期：1996.1

  The anion derived from diethyl α-fluorobenzyl phosphonate (EtO)2P(O)-CFHPh (2) and lithium diisopropylamide in THF underwent the reaction with aldehydes and ketones to afford a moderate to good yields of phenyl substituted fluoro-olefins RR′C=CFPh (6).

  α-氟代苄基膦酸二乙酯（EtO）2 P（O）-CFHPh（2）和二异丙基氨基化锂在THF中的阴离子与醛和酮反应制得中等至良好收率的苯基取代的氟代烯烃RR'C ＝ CFPh（6）。
• 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.
• 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.
• 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.