(E)-3-phenyl-2-(p-tolyl)acrylic acid

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (E)-3-phenyl-2-(p-tolyl)acrylic acid
• 英文别名: α--trans-zimtsaeure；α-p-Tolyl-trans-zimtsaeure；cis-β-Phenyl-α-<4-methyl-phenyl>-acrylsaeure, trans-α-<4-Methyl-phenyl>-zimtsaeure；(E)-2-(4-methylphenyl)-3-phenylprop-2-enoic acid
• 化学式: C₁₆H₁₄O₂
• 分子量: 238.286
• InChiKey: WWMNOZJOFORCMO-RVDMUPIBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-3-phenyl-2-(p-tolyl)acrylic acid 在 草酰氯 、 N,N-二甲基甲酰胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成
  参考文献：
  名称：

  用Selectfluor进行α，β-不饱和酰胺的立体定向亲电氟环化

  摘要：

  通过正式的卤代环化过程，开发了一种高效的α，β-不饱和酰胺的氟环化方法。该反应在无过渡金属的条件下进行，并导致形成具有优异的区域和非对映选择性的氟化恶唑烷-2,4-二酮。基于初步实验和密度泛函理论计算对反应机理的评估表明，发生了协同的顺-氧代氟化反应，随后发生了反-氧代取代反应。该反应打开了立体特异性氟官能化领域的新窗口。

  DOI：

  10.1021/acs.orglett.0c00620
• 作为产物：
  描述：

  对甲基苯乙酸 、 苯甲醛 在 乙酸酐 、 三乙胺 作用下， 以41%的产率得到(E)-3-phenyl-2-(p-tolyl)acrylic acid
  参考文献：
  名称：

  用Selectfluor进行α，β-不饱和酰胺的立体定向亲电氟环化

  摘要：

  通过正式的卤代环化过程，开发了一种高效的α，β-不饱和酰胺的氟环化方法。该反应在无过渡金属的条件下进行，并导致形成具有优异的区域和非对映选择性的氟化恶唑烷-2,4-二酮。基于初步实验和密度泛函理论计算对反应机理的评估表明，发生了协同的顺-氧代氟化反应，随后发生了反-氧代取代反应。该反应打开了立体特异性氟官能化领域的新窗口。

  DOI：

  10.1021/acs.orglett.0c00620

文献信息

• Palladium-Catalyzed Highly Regioselective Hydrocarboxylation of Alkynes with Carbon Dioxide
  作者：Wenfang Xiong、Fuxing Shi、Ruixiang Cheng、Baiyao Zhu、Lu Wang、Pengquan Chen、Hongming Lou、Wanqing Wu、Chaorong Qi、Ming Lei、Huanfeng Jiang

  DOI：10.1021/acscatal.0c01687

  日期：2020.7.17

  with high regioselectivity under mild reaction conditions. Experimental and DFT mechanistic studies revealed that this reaction proceeded via the cyclopalladation process of alkynes and carbon dioxide in the presence of binap to generate a five-membered palladalactone intermediate and enabled the formation of Markovnikov adducts. Moreover, this strategy provided an effective method for the late-stage

  已经建立了Pd催化的炔烃与二氧化碳的高度区域选择性加氢羧化反应。通过Pd（PPh 3）4的组合和2,2'-双（二苯基膦基）-1,1'-联萘（binap），可以利用各种功能化的炔烃，包括芳基炔烃，脂族炔烃，炔丙基胺和炔丙基醚，来提供多种α -丙烯酸在温和的反应条件下具有高的区域选择性和高收率。实验和DFT机理研究表明，该反应通过在binap存在下炔烃和二氧化碳的环palpalladation过程进行，生成五元的palladalactone中间体，并能够形成马尔可夫尼科夫加合物。此外，该策略为含炔烃的复杂分子（包括天然产物和药物）的后期功能化提供了有效的方法。
• Reactions of Carbonyl Compounds in Basic Solutions. Part 34. The Mechanism of the Base-Catalysed Ring Fission of 2,3-Diphenylcycloprop-2-en-1-one
  作者：Keith Bowden、Emma J. Burgess

  DOI：10.1135/cccc19991594

  日期：——

  The rate coefficients for the base-catalysed ring fission of a series of 2-phenyl-3-(2-, 3- or 4-substituted phenyl)cycloprop-2-en-1-ones to give the corresponding (E)-2,3-diphenylacrylic acids have been determined in water at 30.0 °C, as well as for the unsubstituted compound at 40.0, 50.0 and 60.0 °C. The effects of meta- and para-substituents on the rates have been correlated using the Hammett equation to give a reaction constant, ρ, equal to ca 1.2 at 30 °C. For the unsubstituted compound, the activation parameters have been calculated and the kinetic solvent isotope effect has been studied. The effects of ortho-substituents on the rates appear to be mainly polar, rather than steric, in origin. The evidence indicates a mechanistic pathway which proceeds by addition of hydroxide anion to the ketone, which is rate-determining. The adduct suffers ring fission to give the final product via a carbanionic intermediate.

  一系列2-苯基-3-(2-, 3- 或 4-取代苯基)环丙烯酮在30.0°C的水中的碱催化环裂速率系数已确定，以及未取代化合物在40.0、50.0和60.0°C的速率系数。利用Hammett方程相关了对速率的间位和对位取代基的影响，得到在30°C时等于约1.2的反应常数ρ。对于未取代化合物，已计算了活化参数并研究了动力学溶剂同位素效应。取代基对速率的影响似乎主要是极性的，而不是立体的。证据表明，该机理途径通过氢氧根离子加成到酮中，这是决定速率的步骤。该加合物经历环裂，生成最终产物，通过一个碳负离子中间体。
• Pd-Catalyzed Dehydrogenative Aryl–Aryl Bond Formation via Double C(sp²)–H Bond Activation: Efficient Synthesis of [3,4]-Fused Oxindoles
  作者：Ala Bunescu、Tiffany Piou、Qian Wang、Jieping Zhu

  DOI：10.1021/ol503442n

  日期：2015.1.16

  A Pd(0)-catalyzed double cyclization of easily available o-bromoanilides leading to strained [3,4]-fused oxindoles was developed. The reaction proceeded through a highly ordered sequence involving key carbopalladation, 1,4-Pd migration, and C(sp2)–H functionalization steps.

  开发了Pd（0）催化的容易获得的邻溴代苯甲酰苯胺的双环化反应，导致应变的[3,4]稠合的吲哚。该反应通过一个高度有序的过程进行，该过程涉及关键的碳pal触，1,4-Pd迁移和C（sp 2）–H官能化步骤。
• Synthesis and &lt;i&gt;In-Vitro&lt;/i&gt; Cytotoxicity of (E)-N,2,3-Triarylacrylamide Derivatives as Analogs of Combretastatin A-4
  作者：Kun-Ming Jiang、Xiao-Li Dai、Ke Li、Di Wu、Ji-Hong Zhang、Yi Jin、Jun Lin

  DOI：10.2174/1573406410666141226132926

  日期：2015.6.30

  A new series of (E)-N,2,3-triarylacrylamide derivatives were designed and synthesized as potent anticancer agents. Cytotoxicity of the 26 target compounds was evaluated in vitro against six cancer cell lines (HCT116, A549, MDA-MB-468, HepG2, SKNMC and SK-OV-3) by Sulforhodamine B colorimetric assay. The most promising compound, 4h, was as potent as the reference drug cisplatin (DDP). Preliminary structure–activity relationship (SAR) data provided guidance for further design and discovery of (E)- N,2,3-triarylacrylamide scaffold anticancer agents.

  研究人员设计并合成了一系列新的（E）-N,2,3-三芳基丙烯酰胺衍生物，作为强效抗癌剂。通过磺基罗丹明 B 比色法，体外评估了 26 种目标化合物对六种癌细胞株（HCT116、A549、MDA-MB-468、HepG2、SKNMC 和 SK-OV-3）的细胞毒性。最有希望的化合物 4h 与参考药物顺铂（DDP）具有同样的药效。初步的结构-活性关系（SAR）数据为进一步设计和发现(E)-N,2,3-三芳基丙烯酰胺支架抗癌剂提供了指导。
• Structural requirements for substrate in highly enantioselective hydrogenation over the cinchonidine-modified Pd/C
  作者：Takashi Sugimura、Takayuki Uchida、Junya Watanabe、Takeshi Kubota、Yasuaki Okamoto、Tomonori Misaki、Tadashi Okuyama

  DOI：10.1016/j.jcat.2008.11.022

  日期：2009.2.15

  Relationship between substrate Structure and enantioselectivity is studied for the asymmetric hydrogenation of 42 different (E)-alpha, beta-disubstituted acrylic acids (propenoic acids) over cinchonidine-modified Pd/C. The beta-phenyl group is indispensable for high enantioselectivity of alpha-phenylcinnamic acid (2,3-diphenylpropenoic acid, 81% ee), and substitution on this group affects markedly the selectivity. The high ee up to 92% was achieved by the beta-p-alkoxyphenyl substitution, and the selectivity is ascribed mainly to stronger interaction of the substrate with the chiral modifier on the catalyst surface. In contrast, substitution on the alpha-phenyl group does not affect notably the enantioselectivity (80-82% ee) or even the alpha-phenyl group itself is not indispensable but replaceable with a properly bulky group for the high enantioselectivity, (C) 2008 Elsevier Inc. All rights reserved.