ethyl (Z)-3-(4-(trifluoromethyl)phenyl)but-2-enoate | 581812-95-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: ethyl (Z)-3-(4-(trifluoromethyl)phenyl)but-2-enoate
• 英文别名: ethyl (Z)-3-[4-(trifluoromethyl)phenyl]but-2-enoate
• CAS: 581812-95-5
• 化学式: C₁₃H₁₃F₃O₂
• 分子量: 258.24
• InChiKey: SBBOWUUUTVPICX-HJWRWDBZSA-N

物化性质

• 沸点：
  281.9±35.0 °C(Predicted)
• 密度：
  1.172±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl (Z)-3-(4-(trifluoromethyl)phenyl)but-2-enoate 在 sodium hydroxide 作用下， 以 乙醇 、 水 为溶剂， 反应 16.0h， 以80%的产率得到(Z)-3-(4-(trifluoromethyl)phenyl)but-2-enoic acid
  参考文献：
  名称：

  一种光催化剂，用于级联催化的 n 活化模式策略：用 (-)-核黄素模拟香豆素生物合成

  摘要：

  使用单一催化剂产生分子复杂性，其中必要的活化模式随着反应的进行而依次利用，是合成中一个有吸引力的指导原则。这要求每个底物转位都暴露出一种催化剂活化模式 (AM)，所有先前或未来的中间体都对这种模式具有抵抗力。虽然麦克米伦将烯胺和亚胺离子活化的美丽结合体现了这一概念，但当代催化其他领域的例子仍然难以捉摸。在这里，我们将此策略扩展到有机光化学。通过利用 (-)-核黄素的两种离散光化学活化模式，可以分别通过能量转移 (ET) 和单电子转移 (SET) 激活途径依次诱导异构化和环化。这种催化方法已被用于模拟香豆素生物合成途径，该途径具有关键的光化学 E → Z 异构化步骤。由于随后的基于 SET 的环化消除了对预官能化芳环的需要，这构成了药学重要支架的新断开连接。

  DOI：

  10.1021/jacs.5b12081
• 作为产物：
  描述：

  4'-三氟甲基苯乙酮 在 sodium hydride 、 维生素 B2 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 24.0h， 生成 ethyl (Z)-3-(4-(trifluoromethyl)phenyl)but-2-enoate
  参考文献：
  名称：

  A Bio-Inspired, CatalyticE→ZIsomerization of Activated Olefins

  摘要：

  Herein, Nature's flavin-mediated activation of complex (poly)enes has been translated to a small molecule paradigm culminating in a highly (Z)-selective, catalytic isomerization of activated olefins using (-)-ribo-flavin (up to 99:1 Z/E). In contrast to the prominent Z -> E isomerization of the natural system, it was possible to invert the directionality of the isomerization (E -> Z) by simultaneously truncating the retinal scaffold, and introducing a third olefin substituent to augment A1,3-strain upon isomerization. Consequently, conjugation is reduced in the product chromophore leading to a substrate/product combination with discrete photophysical signatures. The operationally simple isomerization protocol has been applied to a variety of enone-derived substrates and showcased in the preparation of the medically relevant 4-substituted coumarin scaffold. A correlation of sensitizer triplet energy (ET) and reaction efficiency, together with the study of additive effects and mechanistic probes, is consistent with a triplet energy transfer mechanism.

  DOI：

  10.1021/jacs.5b07136

文献信息

• Fused azabicyclic compounds that inhibit vanilloid receptor subtype 1 (VR1) receptor
  申请人：Lee Chih-Hung

  公开号：US20050113576A1

  公开（公告）日：2005-05-26

  Compounds of formula (I) are novel VR1 antagonists that are useful in treating pain, inflammatory thermal hyperalgesia, urinary incontinence and bladder overactivity.

  公式（I）的化合物是一类新颖的VR1拮抗剂，可用于治疗疼痛、炎症性热超敏痛、尿失禁和膀胱过度活动。
• A Multicomponent Ni-, Zr-, and Cu-Catalyzed Strategy for Enantioselective Synthesis of Alkenyl-Substituted Quaternary Carbons
  作者：Kevin P. McGrath、Amir H. Hoveyda

  DOI：10.1002/anie.201309456

  日期：2014.2.10

  of alkenyl groups to acyclic trisubstituted enones, an advance achieved by adopting an easily modifiable and fully catalytic approach. The requisite alkenylaluminum reagents are synthesized with exceptional site‐ and/or stereoselectivity by a Ni‐catalyzed hydroalumination process, and the necessary enones are prepared through a site‐ and stereoselective zirconocene‐catalyzed carboalumination/acylation

  富含对映体的含羰基化合物的可用性对于生物活性分子的合成至关重要。由于催化对映选择性共轭加成 (ECA) 反应直接生成后一类有价值的分子，因此此类方案的设计和开发代表了现代化学中一个引人注目的目标。在此，我们公开了烯基到无环三取代烯酮的 ECA 问题的第一个解决方案，这是通过采用易于修改和完全催化的方法取得的进展。通过镍催化的加氢铝化过程合成了具有特殊位点和/或立体选择性的所需烯基铝试剂，并通过位点和立体选择性二茂锆催化的碳铝化/酰化反应制备了必要的烯酮。全催化过程在四小时内完成，以高达 77% 的总产率和 99:1 的对映体比例提供所需的产物。
• Ir-Catalyzed Asymmetric Allylic Alkylation of Dialkyl Malonates Enabling the Construction of Enantioenriched All-Carbon Quaternary Centers
  作者：Farbod A. Moghadam、Elliot F. Hicks、Zachary P. Sercel、Alexander Q. Cusumano、Michael D. Bartberger、Brian M. Stoltz

  DOI：10.1021/jacs.2c02960

  日期：2022.5.11

  An enantioselective iridium-catalyzed allylic alkylation of malonates with trisubstituted allylic electrophiles to form all-carbon quaternary stereocenters is reported. This reaction proceeds at ambient temperature and enables the preparation of a wide range of enantioenriched products in up to 93% yield and 97% ee. The quaternary products can be readily converted to several valuable building blocks

  报道了丙二酸酯与三取代的烯丙基亲电子试剂形成全碳季立构中心的对映选择性铱催化的烯丙基烷基化。该反应在环境温度下进行，能够以高达 93% 的产率和 97% 的 ee 制备范围广泛的对映体富集产品。季产品可以很容易地转化为几种有价值的结构单元，例如邻位季产品和 β-季酸。
• Corrigendum: A Multicomponent Ni-, Zr-, and Cu-Catalyzed Strategy for Enantioselective Synthesis of Alkenyl-Substituted Quaternary Carbons
  作者：Kevin P. McGrath、Amir H. Hoveyda

  DOI：10.1002/anie.201407837

  日期：2014.10.6
• A Bio-Inspired, Catalytic<i>E</i>→<i>Z</i>Isomerization of Activated Olefins
  作者：Jan B. Metternich、Ryan Gilmour

  DOI：10.1021/jacs.5b07136

  日期：2015.9.9

  Herein, Nature's flavin-mediated activation of complex (poly)enes has been translated to a small molecule paradigm culminating in a highly (Z)-selective, catalytic isomerization of activated olefins using (-)-ribo-flavin (up to 99:1 Z/E). In contrast to the prominent Z -> E isomerization of the natural system, it was possible to invert the directionality of the isomerization (E -> Z) by simultaneously truncating the retinal scaffold, and introducing a third olefin substituent to augment A1,3-strain upon isomerization. Consequently, conjugation is reduced in the product chromophore leading to a substrate/product combination with discrete photophysical signatures. The operationally simple isomerization protocol has been applied to a variety of enone-derived substrates and showcased in the preparation of the medically relevant 4-substituted coumarin scaffold. A correlation of sensitizer triplet energy (ET) and reaction efficiency, together with the study of additive effects and mechanistic probes, is consistent with a triplet energy transfer mechanism.