2-ethyl-4-phenylbuta-2,3-dienoic acid | 52248-51-8

• 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: 2-ethyl-4-phenylbuta-2,3-dienoic acid
• CAS: 52248-51-8
• 化学式: C₁₂H₁₂O₂
• 分子量: 188.226
• InChiKey: MKHKAAZADQEGPF-UHFFFAOYSA-N

物化性质

• 沸点：
  372.2±12.0 °C(Predicted)
• 密度：
  1.087±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.72
• 重原子数：
  14.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  2-ethyl-4-phenylbuta-2,3-dienoic acid 、 3-溴丙炔 在 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 24.0h， 以84%的产率得到prop-2'-ynyl 2-ethyl-4-phenylbuta-2,3-dienoate
  参考文献：
  名称：

  trans-RhCl(CO)(PPh₃)₂-Catalyzed Monomeric and Dimeric Cycloisomerization of Propargylic 2,3-Dienoates. Establishment of α,β-Unsaturated δ-Lactone Rings by Cyclometallation

  摘要：

  Cyclometallation of two unsaturated carbon-carbon bonds usually requires the application of low-valent metal catalysts, which could cleave the propargylic ester linkage. Thus, it is desirable to identify a catalyst which could undergo cyclometallation without cleaving the propargylic ester linkage. In this paper, we used trans-RhCI(CO)(PPh3)(2) to realize the cyclometallation of propargylic 2,3-dienoates. The substituents at the 4-position of allenoate moiety nicely control the reaction pathway: when the 4-position of propargylic 2,3-dienoate 1 was monosubstituted with an aryl group, the bicyclic intermediate 7 formed by the cyclometallation could highly selectively undergo carbometalation with the alkyne moiety in the second molecule of propargylic 2,3-dienoate 1 to afford metallabicyclic intermediates 8a or 8b. Subsequent reductive elimination would afford 9, which could undergo an intramolecular Diels-Alder reaction resulting in the formation of polycyclic bis(delta-lactone)-containing structures 2. The intermediate could be trapped by adding 3-methoxyprop-1-yne affording cyclization-aromatization product 4p highly selectively. If the substituent at the 4-positon of the 2,3-allenoate moiety has a beta-H atom, sequential unimolecular cyclometallation/beta-H elimination/reductive elimination occurs to afford cross-conjugated 5(Z)-alkylidene-4-alkenyl-5,6-dihydropyran-2-ones. The Z-stereochemistry of the exo double bond was determined by the cyclometallation. Some of the a,p-unsaturated delta-lactones could be easily converted to other synthetically useful compounds via reduction reaction, hydrogenation, and iodination/coupling protocol.

  DOI：

  10.1021/ja073582u
• 作为产物：
  描述：

  ethyl 2-ethyl-4-phenylbuta-2,3-dienoate 在 水 、 sodium hydroxide 作用下， 以 乙醇 为溶剂， 以38 %的产率得到2-ethyl-4-phenylbuta-2,3-dienoic acid
  参考文献：
  名称：

  季碳中心对映选择性构建中烯醇锂与锂-炔相互作用：(+)-Goniomitine 的简明合成

  摘要：

  我们报道了一种直接对映选择性烷基化形成四级立体中心的 3-炔酸和 2,3-链烯二酸的方法，并将该方法应用于复杂生物碱 (+)-goniomitine 的全对映选择性合成。晶体学研究强调了手性锂聚集中间体中锂和炔基之间的阳离子-π相互作用。

  DOI：

  10.1002/anie.202209987

文献信息

• Palladium Acetate-Catalyzed Cyclization Reaction of 2,3-Allenoic Acids in the Presence of Simple Allenes: An Efficient Synthesis of 4-(1‘-Bromoalk-2‘(<i>Z</i>)-en-2‘-yl)furan-2(5<i>H</i>)-one Derivatives and the Synthetic Application
  作者：Zhenhua Gu、Xinke Wang、Wei Shu、Shengming Ma

  DOI：10.1021/ja072790j

  日期：2007.9.1

  We have realized a cyclization reaction of 2,3-allenoic acids 1 in the presence of simple alkyl- or aryl-substituted allenes 3. In this reaction, the cyclic oxypalladation of 2,3-allenoic acid with Pd(II) would afford the furanonyl palladium intermediate 2, which could be trapped by the simple allene to afford a pi-allylic intermediate anti-9. This intermediate anti-9 could be nucleophilically attacked

  我们已经在简单的烷基或芳基取代的丙二烯 3 存在下实现了 2,3-丙烯酸 1 的环化反应。在该反应中，2,3-丙烯酸与 Pd(II) 的环氧基钯化反应将得到呋喃基钯中间体 2，它可以被简单的丙二烯捕获，得到 pi-烯丙基中间体 anti-9。这种中间体 anti-9 可以被 Br- 亲核攻击以产生 4-(1'-bromOAlk-2'(Z)-en-2'-yl)furan-2(5H)-one 衍生物 Z-5 和 Pd( 0）。苯醌在 HOAc 中有效地将原位形成的 Pd(0) 转化为具有催化活性的 Pd(II) 物质。在当前条件下，丙二酸、乙酰氧基和邻苯二甲酰胺中的丙二酸、邻苯二甲酰胺等官能团是可以接受的。当使用光学活性的 2,3-丙二烯酸时，观察到手性转移的高效率，这表明中间体 2 的形成是一个高度立体选择性的抗氧化钯化过程。Z-异构体的高度选择性形成可以通过丙二烯3与中间体2中的钯原子的面
• Runge,W. et al., Justus Liebigs Annalen der Chemie, 1975, p. 1361 - 1378
  作者：Runge,W. et al.

  DOI：——

  日期：——
• Pd(OAc)₂-Catalyzed Cyclization of 2,3-Allenoic Acids in the Presence of Terminal α,β-Unsaturated Alkynones: A One-Pot Highly Stereoselective Synthesis of 4-(3′-Oxo-1′(<i>E</i>)-alkenyl)-2(5<i>H</i>)-furanones
  作者：Guofei Chen、Rong Zeng、Zhenhua Gu、Chunling Fu、Shengming Ma

  DOI：10.1021/ol801610w

  日期：2008.10.2

  The Pd(OAc)(2)-catalyzed cyclization reaction of 2,3-allenoic acids in the presence of terminal alpha,beta-unsaturated alkynones afforded an E/Z mixture of 4-(3'-oxo-1'-alkenyl)-2(5H)-furanones. A subsequent complete isomerization of the Z-isomer to E-isomer was observed in DMSO at 90 degrees C, which led to a highly stereoselective synthesis of 4-(3'-oxo-1'(E)-alkenyl)-2(5H)-furanones. A possible mechanism is proposed.
• Pd(OAc)2-Catalyzed Coupling/Cyclization of 2,3-Allenoic Acids and Methyl Propiolate: Observation of Double 1,7-Hydrogen Shifts
  作者：Zhenhua Gu、Shengming Ma

  DOI：10.1002/anie.200601699

  日期：2006.9.11