3-(2-aminophenyl)-1-(4-tert-butylcyclohex-1-en-1-yl)prop-2-yn-1-one | 929602-08-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 3-(2-aminophenyl)-1-(4-tert-butylcyclohex-1-en-1-yl)prop-2-yn-1-one
• 英文别名: 3-(2-Aminophenyl)-1-(4-tert-butylcyclohexen-1-yl)prop-2-yn-1-one；3-(2-aminophenyl)-1-(4-tert-butylcyclohexen-1-yl)prop-2-yn-1-one
• CAS: 929602-08-4
• 化学式: C₁₉H₂₃NO
• 分子量: 281.398
• InChiKey: WKSXCMNIGMBECZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  43.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-(2-aminophenyl)-1-(4-tert-butylcyclohex-1-en-1-yl)prop-2-yn-1-one 在 silver trifluoromethanesulfonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.27h， 生成 4-(tert-butyl)cyclohex-1-enyl indol-2-yl ketone
  参考文献：
  名称：

  Ag和Cu催化β-（2-氨基苯基）-α，β-炔酮的抗迈克尔加氢合成2-环戊二烯：实验结果和DFT计算

  摘要：

  在（微波）MW加热下，在20mol％AgOTf的存在下，β-（2-氨基苯基）-α，β-炔酮以良好的产率提供了3-未取代的2-酰基吲哚。使用CuOTf作为催化剂导致相似的反应结果，通常具有较低的效率。这种转化代表了5 -endo-dig的第一个例子带有连接到三键的酰基的2-炔基苯胺的环化。与先前报道的β-（2-氨基苯基）-α，β-炔酮的金催化反应相反，该反应通过分子间氢胺化引发的顺序过程导致了二苯并[1,5]重氮电影的形成。在本研究中，通过银/铜催化观察到了分子内抗迈克尔加氢胺化反应。对Ag催化的反应的密度泛函理论计算表明，该催化剂在与实验观察到的环化一致的TS中诱导了静电排列。

  DOI：

  10.1021/acs.joc.8b00508
• 作为产物：
  描述：

  2-氨基苯乙炔 、 一氧化碳 、 1-trifluoromethanesulfonyloxy-4-t-butylcyclohexene 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70%的产率得到3-(2-aminophenyl)-1-(4-tert-butylcyclohex-1-en-1-yl)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

• Gold-Catalyzed Synthesis of Dibenzo[1,5]diazocines from β-(2-Aminophenyl)-α,β-ynones
  作者：Navnath D. Rode、Antonio Arcadi、Marco Chiarini、Fabio Marinelli、Gustavo Portalone

  DOI：10.1002/adsc.201700694

  日期：2017.10.4

  means of (JonPhosAuNCMe)SbF6 catalysis. In contrast with the known gold-catalyzed reaction path of 2-alkynylanilines that leads to indoles, ynones underwent an auto intermolecular hydroamination. This process resulted finally in the formation of an eight-membered ring, likely through a selective 8-exo-dig intramolecular hydroamination that prevailed over the possible cyclocondensation reaction (that

  β-（2-氨基苯基）-α，β-炔酮通过（JonPhosAuNCMe）SbF 6催化提供了具有挑战性的二苯并[1,5]重氮化合物。与导致吲哚的2-炔基苯胺的金催化的反应路径相反，炔酮经历了自分子间加氢胺化反应。此过程最终导致了八元环的形成，可能是通过选择性的8-exo-dig可能发生的环缩合反应（这会导致形成4-氨基喹啉衍生物）占主导地位的分子内加氢胺化作用。β-（2-氨基苯基）-α，β-炔酮的易得性和简单的环化程序使该方法适用于制备各种有用的二苯并重氮化合物。该方法可以扩展到使用β-（2-氨基苯基）-α，β-叶酸酯作为底物。
• 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。
• 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
  作者：Antonio Arcadi、Massimiliano Aschi、Fabio Marinelli、Mirella Verdecchia

  DOI：10.1016/j.tet.2008.03.015

  日期：2008.5

  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.
• Synthesis of 2-Acylindoles via Ag- and Cu-Catalyzed anti-Michael Hydroamination of β-(2-Aminophenyl)-α,β-ynones: Experimental Results and DFT Calculations
  作者：Navnath D. Rode、Issam Abdalghani、Antonio Arcadi、Massimiliano Aschi、Marco Chiarini、Fabio Marinelli

  DOI：10.1021/acs.joc.8b00508

  日期：2018.6.15

  acyl group linked to the triple bond. By contrast with the previously reported gold-catalyzed reaction of β-(2-aminophenyl)-α,β-ynones, which resulted in the formation of dibenzo[1,5]diazocines through a sequential process triggered by an intermolecular hydroamination, a selective intramolecular anti-Michael hydroamination was observed in the present study by silver/copper catalysis. Density functional

  在（微波）MW加热下，在20mol％AgOTf的存在下，β-（2-氨基苯基）-α，β-炔酮以良好的产率提供了3-未取代的2-酰基吲哚。使用CuOTf作为催化剂导致相似的反应结果，通常具有较低的效率。这种转化代表了5 -endo-dig的第一个例子带有连接到三键的酰基的2-炔基苯胺的环化。与先前报道的β-（2-氨基苯基）-α，β-炔酮的金催化反应相反，该反应通过分子间氢胺化引发的顺序过程导致了二苯并[1,5]重氮电影的形成。在本研究中，通过银/铜催化观察到了分子内抗迈克尔加氢胺化反应。对Ag催化的反应的密度泛函理论计算表明，该催化剂在与实验观察到的环化一致的TS中诱导了静电排列。