3-(2-amino-3,5-difluorophenyl)-1-(2-methoxyphenyl)prop-2-yn-1-one | 929602-07-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: 3-(2-amino-3,5-difluorophenyl)-1-(2-methoxyphenyl)prop-2-yn-1-one
• CAS: 929602-07-3
• 化学式: C₁₆H₁₁F₂NO₂
• 分子量: 287.266
• InChiKey: XZYCZVQRBABQJD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  21
• 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：
  52.3
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-(2-amino-3,5-difluorophenyl)-1-(2-methoxyphenyl)prop-2-yn-1-one 在 四(三苯基膦)钯 、 potassium carbonate 、 对甲苯磺酸 、 sodium iodide 作用下， 以 乙醇 为溶剂， 反应 7.5h， 生成 ethyl 3-{3-[6,8-difluoro-2-(2-methoxyphenyl)quinolin-4-yl]-1H-indol-2-yl}benzoate
  参考文献：
  名称：

  一种简单的一锅法合成4-（1H-吲哚-3-基）喹啉

  摘要：

  一个操作简单的过程，涉及将NaI与2-炔基-三氟乙酰苯胺共轭加成至β-（2-氨基苯基）-α，β-炔酮/环化/ Pd催化的反应，得到4-（1 H-吲哚-3-基）喹啉。整个过程在同一烧瓶中进行，无需任何中间处理，并使用乙醇作为溶剂。 环化-钯-喹啉-吲哚-杂环-一锅反应

  DOI：

  10.1055/s-0031-1289589
• 作为产物：
  描述：

  一氧化碳 、 2-乙炔基-4,6-二氟苯胺 、 alkaline earth salt of/the/ methylsulfuric acid 在 palladium dichloride 1,1'-双(二苯基膦)二茂铁 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 20.0 ℃ 、1.0 MPa 条件下， 以76%的产率得到3-(2-amino-3,5-difluorophenyl)-1-(2-methoxyphenyl)prop-2-yn-1-one
  参考文献：
  名称：

  Pd-catalyzed regioselective hydroarylation of α-(2-aminoaryl)-α,β-ynones with organoboron derivatives as a tool for the synthesis of quinolines: experimental evidence and quantum-chemical calculations

  摘要：

  The Pd-catalyzed hydroarylation of beta-(2-aminoaryl)-alpha,beta-ynones with organoboron derivatives, leading to 2,4-diarylquinolines in good to excellent yields through sequential cycloamination, has been investigated. The reaction is catalyzed by both Pd(II) and Pd(0) precatalysts, and can be carried out even under neutral conditions. The regiochemical outcome is inverted with respect to the Pd-catalyzed hydroarylation of beta-(2-aminoaryl)-alpha,beta-ynones with aryl iodides. This aspect has been rationalized using quantum-chemical calculations, which show significant differences between the energy barriers of the regioisomeric transition states for the migratory insertion (hydropalladation) step, and are consistent with the charge density of the pi complex that undergoes such insertion. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.03.015

文献信息

• Sequential 1,3-Dipolar Cycloaddition of Nitrones to β-(2-Aminophenyl) α,β-Ynones and Cyclocondensation: A New Entry to the Isoxazolino[4,5-c]quinoline Ring
  作者：Giorgio Abbiati、Antonio Arcadi、Fabio Marinelli、Elisabetta Rossi、Mirella Verdecchia

  DOI：10.1002/ejoc.200800994

  日期：2009.3

  The reaction of β-(2-aminophenyl) α,β-ynones with N-methyl nitrones provides a simple and efficient entry to the isoxazolino[4,5-c]quinoline ring system through a sequential 1,3-dipolar cycloaddition/annulation process. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

  β-(2-氨基苯基) α,β-炔酮与 N-甲基硝酮的反应通过连续的 1,3-偶极环加成/环化提供了一种简单有效的进入异恶唑并[4,5-c]喹啉环系统的方法过程。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Synthesis of Polycyclic Quinolines by Means of Brønsted Acid Mediated Reaction of β‐(2‐Aminophenyl)‐α,β‐Ynones with Ketones
  作者：Vincenzo Marsicano、Marco Chiarini、Fabio Marinelli、Antonio Arcadi

  DOI：10.1002/adsc.201900141

  日期：2019.5.14

  Sequential Brønsted acid promoted amination/annulation/aromatization of β‐(2‐aminophenyl)‐α,β‐ynones with cyclic α‐methylene carbonyl compounds has been developed for the synthesis of polycyclic quinolines in good to high yields in ethanol. The protocol achieves the selective formation of the target quinolines and is expected to find practical applications due to its operational simplicity.

  已开发出顺序的布朗斯台德酸促进β-（2-氨基苯基）-α，β-酮与环状α-亚甲基羰基化合物的胺化/环化/芳构化，可在乙醇中以高收率或高收率合成多环喹啉。该协议实现了目标喹啉的选择性形成，并且由于其操作简便性，有望用于实际应用。
• Sequential Alkylation/Heterocyclization of β-(2-Aminophenyl)-α,β-ynones Promoted by Electrogenerated Carbanions: A New Approach to ­Functionalized 4-Alkylquinolines
  作者：Antonio Arcadi、Leucio Rossi、Gabriele Bianchi、Achille Inesi、Fabio Marinelli

  DOI：10.1055/s-2007-973891

  日期：2007.4

  Electrolysis in a divided cell (nitroalkanes or methanol, in the absence of solvent and supporting electrolyte, as catholite) gave functionalized 4-alkylquinolines in moderate to high yields through a sequential alkylative heterocyclization of β-(2-amino­phenyl)-α,β-ynones. The sequential alkylative heterocyclization process can be extended to the reaction of β-(2-aminophenyl)-α,β-ynones with 1,3-dicarbonyls by galvanostatic electrolysis of these latter derivatives in a tetraethylammonium tetrafluoroborate-N,N-dimethylformamide solution.

  通过δ-(2-氨基苯基)-δ,δ-炔酮的序贯烷基化杂环反应，在分层电池（硝基烷烃或甲醇，无溶剂和支撑电解质，如阴极石）中进行电解，可得到中高产率的官能化 4-烷基喹啉。通过在四氟硼酸四乙基铵-N,N-二甲基甲酰胺溶液中对δ²-(2-氨基苯基)-δ,δ-炔酮与 1,3-二羰基的电解，可以将顺序烷基化杂环化过程扩展到δ²-(2-氨基苯基)-δ,δ-炔酮与 1,3-二羰基的反应。
• Rh-Catalyzed Sequential Hydroarylation/Hydrovinylation-Heterocyclization of β-(2-Aminophenyl)-α,β-ynones with Organoboron Derivatives: A New Approach to Functionalized Quinolines
  作者：Fabio Marinelli、Giorgio Abbiati、Antonio Arcadi、Elisabetta Rossi、Mirella Verdecchia

  DOI：10.1055/s-2006-956462

  日期：——

  4-Aryl and 4-vinyl quinolines were prepared via a sequential procedure involving regioselective Rh(acac)(C2H2)/dppf-catalyzed hydroarylation/hydrovinylation of β-(2-aminophenyl)-α,β-ynones with arylboronic acids or potassium aryl and vinyl trifluoroborates, followed by nucleophilic attack of the amino group onto the carbonyl.

  4-芳基和 4-乙烯基喹啉是通过连续程序制备的，涉及区域选择性 Rh(acac)(C2H2)/dppf 催化的 β-(2-氨基苯基)-α,β-ynones 与芳基硼酸或钾的加氢芳基化/氢乙烯基化芳基和乙烯基三氟硼酸酯，然后氨基对羰基进行亲核攻击。
• Direct Regioselective Hydro(hetero)arylation/Cyclocondensation Reactions of β-(2-Aminophenyl)-α,β-ynones by Means of Transition-Metal Catalysis/Brønsted Acid Synergism: Experimental Results and Computational Insights
  作者：Vincenzo Marsicano、Antonio Arcadi、Massimiliano Aschi、Marco Chiarini、Giancarlo Fabrizi、Antonella Goggiamani、Fabio Marinelli、Antonia Iazzetti

  DOI：10.1021/acs.joc.3c00137

  日期：2023.6.2

  Experimental results and computational insights explain the key role of transition-metal catalysis/Brønsted acid synergism in the achievement of the sequential regioselective direct heteroarylation/cyclocondensation reactions of β-(2-aminophenyl)-α,β-ynones with a variety of electron-rich aromatic heterocyclic/arenes to afford quinoline-(hetero)aromatic hybrids. The first approach to the synthesis

  实验结果和计算见解解释了过渡金属催化/Brønsted 酸协同作用在实现 β-(2-氨基苯基)-α,β-炔酮与各种电子-的顺序区域选择性直接杂芳基化/环缩合反应中的关键作用富含芳香杂环/芳烃以提供喹啉-（杂）芳香杂化物。描述了合成 4-(1 H -pyrrol-2-yl)quinolines 的第一种方法。比较了各种过渡金属的有效性。