Room‐Temperature Practical Copper‐Catalyzed Amination of Aryl Iodides

Abstract

An efficient and highly practical procedure is reported for the Ullmann–Goldberg‐type copper‐catalyzed amination of aryl iodides. By using a combination of copper iodide and proline in the presence of an excess of an amine, a wide range of aryl iodides can be readily aminated at room temperature. The reaction proceeds well regardless of the electronic properties of the starting aryl iodide and the amination products can be obtained without the need for purification by column chromatography in most cases. Owing to its efficiency and the mildness of the reaction conditions, this amination could also be extended to the amination of complex aryl iodides at room temperature.

Recent Advances and Perspectives in the Copper‐Catalysed Amination of Aryl and Heteroaryl Halides

“…A smooth and effective Ullmann‐Goldberg‐like copper‐catalysed protocol for aryl iodide amination was established by Evano and co‐workers . The yield of the desired product was improved to about 71 % by using a combination of 20 mol % CuI and 40 mol % L ‐proline in excess amine conditions.…”

Ausgewählte Kupfer‐katalysierte Reaktionen für die Bildung von C‐N‐, C‐O‐, C‐S‐ und C‐C‐Bindungen

“…Amin als Kupplungspartner und Base die Umsetzung von Aryliodiden mit einer Vielzahl aliphatischer Amine bei Raumtemperatur durchgeführt werden kann (Nr. 9) . Diese mildere Methode kann für die Herstellung von Arylaminen hilfreich sein, die empfindlich gegen stark basische Bedingungen sind.…”

Synthetic and computational studies on CuI/ligand pair promoted activation of C(Aryl)-Cl bond in C–N coupling reactions

“…Usually, Pd-mediated reactions [8] are more efficient than Cu-mediated reactions and have a wider substrate scope (ArX, X ¼ Cl, Br and I). Aryl iodides and aryl bromides are good substrates in Cu-mediated C-heteroatom arylation reactions [9,10,11,12,13,14,15,16] but reactions are not much successful in activation of commercially cheaper aryl chlorides (ArCl) [17] which are easily activated in presence of expensive Pd/ligand and CuI/oxamide ligand system [18]. As compared to Buchwald-Hartwig reaction (Pd-mediated reactions) modern Ullmann reaction has many advantages like simplicity of the ligands, low toxicity of copper and overall low cost of the process.…”