ethyl 2-[(3-cyanophenyl)amino]benzoate

• 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: ethyl 2-[(3-cyanophenyl)amino]benzoate
• 英文别名: 3-cyano-2'-carbethoxydiphenylamine；Ethyl 2-(3-cyanoanilino)benzoate
• 化学式: C₁₆H₁₄N₂O₂
• 分子量: 266.299
• InChiKey: UNIGXEJRNXSPDF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  62.1
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  3-氯苯腈 、 2-氨基苯甲酸乙酯 在 C₅₀H₇₂ClPPd 、 2,6-bis(2,4,6-triisopropylphenyl)phenyldicyclohexylphosphine 、 potassium carbonate 作用下， 以 叔丁醇 为溶剂， 反应 3.0h， 以89%的产率得到ethyl 2-[(3-cyanophenyl)amino]benzoate
  参考文献：
  名称：

  三联苯膦作为钯催化芳基卤与 1°苯胺胺化的高效配体

  摘要：

  已开发出三联苯膦配体（2,6-双（2,4,6-三异丙基苯基）苯基-二环己基膦，TXPhos）及其负载的钯配合物[(TXPhos)(allyl)PdCl]，该催化剂体系在芳基卤化物与 1° 苯胺的胺化，对密集官能化的底物特别有效，包括具有原酸酯、乙酰基、腈和硝基的两个伙伴。使用TXPhos负载的催化剂体系，前所未有地实现了许多合作伙伴的组合，基础范围甚至扩展到了KOAc，这甚至是2-硝基氯苯胺化的最佳选择。

  DOI：

  10.1016/j.jcat.2021.08.017

文献信息

• Selective Palladium-Catalyzed Aminations on 2-Chloro-3-iodo- and 2-Chloro-5-iodopyridine
  作者：Bert U. Maes、Kristof T. Loones、Tim H. Jonckers、Guy L. Lemière、Roger A. Dommisse、Achiel Haemers

  DOI：10.1055/s-2002-35579

  日期：——

  Regioselective palladium-catalyzed aminations with anilines on 2-chloro-3-iodo- and 2-chloro-5-iodopyridine have been performed with excellent yields and good selectivity. The use of a large excess of Cs2CO3 in combination with Pd-BINAP catalyst was essential to obtain sufficiently fast reactions. The mild conditions permit the presence of base sensitive functional groups. Moreover, the catalytic system developed also allows the arylamination of aryl iodides.

  在2-氯-3-碘和2-氯-5-碘吡啶上进行的区域选择性钯催化胺化反应，采用苯胺作为原料，取得了出色的产率和良好的选择性。使用过量的Cs2CO3结合Pd-BINAP催化剂是实现反应足够迅速的关键。温和的反应条件允许存在对碱敏感的官能团。此外，所开发的催化体系还支持芳基碘的芳基化反应。
• An Improved Method for the Palladium-Catalyzed Amination of Aryl Iodides
  作者：Mayssam H. Ali、Stephen L. Buchwald

  DOI：10.1021/jo0008486

  日期：2001.4.1

  Aryl iodides are coupled with amines to give the corresponding arylamines in high yield in the presence of palladium, a suitable ligand, and NaOt-Bu. Functionalized aryl iodides give good yields of the corresponding arylamines when Cs2CO3 is substituted as the base.
• Study of a New Rate Increasing “Base Effect” in the Palladium-Catalyzed Amination of Aryl Iodides
  作者：Caroline Meyers、Bert U. W. Maes、Kristof T. J. Loones、Gunther Bal、Guy L. F. Lemière、Roger A. Dommisse

  DOI：10.1021/jo049774e

  日期：2004.9.1

  Evidence for an interphase deprotonation of Pd(II)-amine complexes with weak carbonate base has been gained for the first time. When a rate-limiting deprotonation step is involved in the catalytic cycle, controlling the structure (shape and size of the particles) and/or molar excess of the carbonate base used can significantly increase the reaction rate of Buchwald-Hartwig aminations. By taking such a "base effect" into account a general protocol for the intermolecular amination of aryl iodides with all types of amines has been developed based on a standard Pd-BINAP catalyst, using cesium carbonate as the base.
• A terphenyl phosphine as a highly efficient ligand for palladium-catalysed amination of aryl halides with 1° anilines
  作者：Fabin Zhou、Lixue Zhang、Ji-cheng Shi

  DOI：10.1016/j.jcat.2021.08.017

  日期：2021.10

  A terphenyl phosphine ligand (2,6-bis(2,4,6-triisopropylphenyl)phenyl-dicyclohexylphosphine, TXPhos) and its supported palladium complex [(TXPhos)(allyl)PdCl] have been developed and the catalyst system is highly efficient in amination of aryl halides with 1° anilines, especially effective for densely functionalized substrates including both partners possessing ortho-ester, acetyl, nitrile and nitro

  已开发出三联苯膦配体（2,6-双（2,4,6-三异丙基苯基）苯基-二环己基膦，TXPhos）及其负载的钯配合物[(TXPhos)(allyl)PdCl]，该催化剂体系在芳基卤化物与 1° 苯胺的胺化，对密集官能化的底物特别有效，包括具有原酸酯、乙酰基、腈和硝基的两个伙伴。使用TXPhos负载的催化剂体系，前所未有地实现了许多合作伙伴的组合，基础范围甚至扩展到了KOAc，这甚至是2-硝基氯苯胺化的最佳选择。