(E)-2-fluoro-3-phenylprop-2-enyl acetate | 400092-11-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-2-fluoro-3-phenylprop-2-enyl acetate
• 英文别名: (E)-2-fluoro-3-phenylbut-2-enyl acetate；(E)-α-fluorocinnamyl acetate；(E)-2-fluoro-3-phenylallyl acetate；2-Methylacetoxy-2-fluoro-1-phenylprop-1-ene；[(E)-2-fluoro-3-phenylprop-2-enyl] acetate
• CAS: 400092-11-7
• 化学式: C₁₁H₁₁FO₂
• 分子量: 194.206
• InChiKey: WMOPGNJNLNIWRQ-YRNVUSSQSA-N

物化性质

• 沸点：
  286.8±35.0 °C(Predicted)
• 密度：
  1.128±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-2-fluoro-3-phenylprop-2-enyl acetate 、 甲基丙二酸二甲酯 在 2,2'-联吡啶 、 [Pd(C₃H₅)(cod)]BF₄ 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 1,4-二氧六环 为溶剂， 反应 12.0h， 以50%的产率得到(E)-tetramethyl 3-benzylidenehexane-2,2,5,5-tetracarboxylate
  参考文献：
  名称：

  Palladium-Catalyzed Double Alkylation of 3-Aryl-2-fluoroallyl Esters with Malonate Nucleophiles through the Carbon–Fluorine Bond Cleavage

  摘要：

  The alkylation of (Z)-3-aryl-2-fluoroallyl acetate with the malonate anion by the [Pd(C3H5)(cod)]BF4/2,2'-bpy catalyst proceeds through the carbon fluorine bond cleavage, and 2 equiv of the malonate nucleophile was introduced to the allyl substrate.

  DOI：

  10.1021/ol500121z
• 作为产物：
  描述：

  ethyl (E)-2-fluoro-3-phenylacrylate 在 二异丁基氢化铝 作用下， 以 四氢呋喃 、 吡啶 、 甲苯 为溶剂， 生成 (E)-2-fluoro-3-phenylprop-2-enyl acetate
  参考文献：
  名称：

  Iridium-Catalyzed Asymmetric Hydrogenation of Fluorinated Olefins Using N,P-Ligands:  A Struggle with Hydrogenolysis and Selectivity

  摘要：

  To broaden the substrate scope of asymmetric iridium-catalyzed hydrogenation, fluorine-functionalized olefins were synthesized and hydrogenated with iridium complexes. Preliminary results showed high levels of fluorine elimination together with low selectivity. The loss of vinylic fluorine at first seemed difficult to handle, but further studies revealed that a catalyst with an azanorbornyl scaffold in the ligand gave more promising results. With this in mind, a new ligand was developed. This gave among the best results published to date for fluorine asymmetric hydrogenation, yielding high conversion and very high ee's with very little fluorine elimination. Further increasing the selectivity, the trials also revealed that tetrasubstituted fluorine-containing olefins can be hydrogenated with high ee's, despite that this class of compounds has usually shown low reactivity in this reaction type.

  DOI：

  10.1021/ja0686763

文献信息

• Iridium Catalysts with Chiral Imidazole-Phosphine Ligands for Asymmetric Hydrogenation of Vinyl Fluorides and other Olefins
  作者：Päivi Kaukoranta、Mattias Engman、Christian Hedberg、Jonas Bergquist、Pher G. Andersson

  DOI：10.1002/adsc.200800062

  日期：2008.5.5

  New chiral bidentate imidazole-phosphine ligands have been prepared and evaluated for the iridium-catalysed asymmetric hydrogenation of olefins. The imidazole-phosphine-ligated iridium catalysts hydrogenated trisubstituted olefins with the same sense of enantiodiscrimination as known iridium catalysts possessing oxazole and thiazole as N-donors. The imidazole-based catalysts were shown to hydrogenate

  制备了新的手性二齿咪唑-膦配体，并进行了铱催化的烯烃不对称氢化的评估。与已知的具有恶唑和噻唑作为N-给体的铱催化剂一样，咪唑-膦连接的铱催化剂以对映异构的相同含义氢化三取代的烯烃。已显示基于咪唑的催化剂可氢化氟乙烯，在某些情况下，迄今公布的ee值最高。
• Palladium-catalyzed intermolecular coupling of 2-haloallylic acetates with simple phenols, and sequential formation of benzofuran derivatives through the intramolecular cyclization
  作者：Takumi Udagawa、Yukiko Tsuchi、Ikuma Takehara、Masaki Kogawa、Hirotaka Watanabe、Mitsuaki Yamamoto、Hiroaki Tsuji、Motoi Kawatsura

  DOI：10.1016/j.tet.2017.10.001

  日期：2017.11

  synthesis of 2-substituted benzofuran derivatives by the palladium-catalyzed reaction of 2-haloallylic acetates with simple phenols in the presence of a base. The reaction proceeded through the intermolecular attack of the nucleophile on the central carbon atom of the π-allyl group, carbon-halogen bond cleavage, and sequential intramolecular cyclization.

  我们在碱的存在下，通过2-卤代烯丙基乙酸盐与简单酚的钯催化反应，完成了2-取代的苯并呋喃衍生物的合成。该反应通过亲核体对π-烯丙基的中心碳原子的分子间攻击，碳-卤素键的裂解以及依次的分子内环化而进行。
• 2-Fluoro-3-phenyl-allyltrimethylsilane: A new fluorinated reagent for Hosomi–Sakurai reaction
  作者：Tsuyoshi Hayashi、Yoshinosuke Usuki、Hideo Iio

  DOI：10.1016/j.jfluchem.2010.03.005

  日期：2010.6

  2-Fluoro-3-phenyl-allyltrimethylsilane, prepared from β-fluorinated allylic acetate via a π-allylpalladium intermediate, reacted with various aldehydes and acetals in the presence of TiCl4 to afford the corresponding homoallyl alcohols and homoallyl ethers, respectively, in good to moderate yields.

  由β-氟化烯丙基乙酸酯经π-烯丙基钯中间体制得的2-氟-3-苯基-烯丙基三甲基硅烷在TiCl 4的存在下与各种醛和缩醛反应，分别制得相应的均烯丙基醇和均烯丙基醚适度的产量。
• Double amination of 2-fluoroallylic acetates by palladium catalysts
  作者：Yukiko Tsuchi、Hirotaka Watanabe、Masaki Kogawa、Biao Zhou、Hiroaki Tsuji、Motoi Kawatsura

  DOI：10.1016/j.tetlet.2018.02.047

  日期：2018.3

  palladium-catalyzed double substitution of 2-haloallylic acetates with nitrogen nucleophiles. During the Pd2(dba)3/DPPE-catalyzed reaction of 2-fluoroallylic acetates with N-substituted-p-toluenesulfonamide, two equivalents of nitrogen nucleophiles were introduced to the allyl unit with a Z-selectivity through the carbon–fluorine bond cleavage. We further demonstrated the reaction of 2-chloroallylic acetates

  我们用氮亲核试剂完成了钯催化的2-卤代烯丙基乙酸酯的双取代。在Pd 2（dba）3 / DPPE催化的2-氟代烯丙基乙酸酯与N-取代的对甲苯磺酰胺的反应中，通过碳-氟键裂解，将两当量的氮亲核试剂以Z选择性引入到烯丙基单元中。。我们进一步证明了2-氯烯丙基乙酸酯的反应，并成功地以高收率和高Z选择性获得了相同的双取代产物。
• Copper(I)-catalyzed solvolysis of gem-chlorofluoro- and gem-bromofluorocyclopropanes. Preparation of 2-fluoroallylic ethers, esters and alcohols
  作者：Maxim A. Novikov、Nikolai V. Volchkov、Maria B. Lipkind、Oleg M. Nefedov

  DOI：10.1016/j.jfluchem.2015.09.001

  日期：2015.12

  Copper(I)-catalyzed solvolysis of gem-chlorofluoro- and gem-bromofluorocyclopropanes in MeOH, NaOAc/AcOH, NaOAc/DMF, HCO2Na/HCO2H or water/dioxane affords 2-fluoroallylic ethers, esters or alcohols in moderate to excellent yields. The reaction pathway involves isomerization of gem-fluorohalocyclopropanes to 2-fluoroallylic halides followed by nucleophilic substitution of a halide onto an O-nucleophile

  铜（I）催化的宝石-氯氟环己烷和宝石-溴氟环丙烷在MeOH，NaOAc / AcOH，NaOAc / DMF，HCO 2 Na / HCO 2 H或水/二恶烷中的溶剂化提供了中等至中度的2-氟烯丙基醚，酯或醇优异的产量。该反应途径涉及宝石-氟卤代环丙烷异构化为2-氟烯丙基卤化物，然后将卤化物亲核取代成O-亲核体。我们在制备合成中开发的方法的适用性在100–200 mmol范围内得到证明。