Simple Copper Salt-Catalyzed N-Arylation of Nitrogen-Containing Heterocycles with Aryl and Heteroaryl Halides

Abstract

Relatively mild and highly efficient CuI-catalyzed N-arylation procedures for nitrogen-containing heterocycles (e.g., imidazoles, benzimidazoles, pyrroles, pyrazoles, indoles, triazoles, etc.) with aryl and heteroaryl halides have been developed. The protocols can be performed easily and tolerate a number of functional groups, such as ester, nitrile, nitro, ketone, free hydroxyl, and free primary amine on the aryl halide.

Sequential Metal‐Catalyzed N‐Heteroarylation and C–C Cross‐Coupling Reactions: An Expedient Route to Tris(hetero)aryl Systems

“…[3d, 8,10,12,15,21] To confirm the versatility of the procedures, analogous reactions are also reported for imidazole (3) and pyrrole (4). The general concept of sequential N-C and C-C couplings leading to tris(hetero)aryl systems is depicted for benzimidazole in Scheme 1.…”

“…(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) process. [15] The CuOAc-mediated N-arylation of indoles and carbazole with aryl iodides under base-free and ligandless conditions has been reported. [16] New developments in palladium- [17] and iron-catalysed [18] N-arylations have also been reported recently.…”

“…analogous reactions with heteroaryl halides. [15] The development of this methodology is, therefore, of considerable interest. Herein we present a series of heterocyclic N-heteroarylation reactions and exploit further reaction at an active halide site in the products via Suzuki-Miyaura cross-coupling reactions leading to the expedient construction of tris(hetero)aryl scaffolds comprising two or three N-heterocyclic rings.…”

[1,3]-Dipolar cycloaddition of N-aryl sydnones to benzothiophene 1,1-dioxide, 1-cyclopropylprop-2-yn-1-ol and 1-(prop-2-ynyl)-1H-indole

“…22 [1,3]-Dipolar cycloadditions of sydnones 1a-g to alkynol 4 in toluene, under reflux, proceeded slowly but smoothly and were also highly regioselective, yielding the regioisomers 5a-g as the only isolable products assignments in general were also supported by the 13 C NMR spectroscopic data. As for carbon chemical shifts of the cycloadducts, the carbon attached to the hydroxyl group resonated at around 72.0 ppm, the pyrazole iminic carbon (C3-pyrazole ring numbering) at around 158-160 ppm and the most shielded aliphatic carbons were the cyclopropyl ring carbons [24][25][26][27] In the mass spectra, while significant molecular ions were observed, the base peaks were due to loss of a molecule of water.…”

N,N′-(Phenylmethylene)diacetamide Analogues as Economical and Efficient Ligands in Copper-Catalyzed Arylation of Aromatic Nitrogen-Containing Heterocycles

“…10 Besides these classical ligands, there are also many novel scaffolds that have been reported as excellent ligands for the copper-catalyzed arylation. For example, N-hydroxy-imides, 11 benzotriazole, 12 hydroxyquinoline, 13 4,7-dimethoxy-1,10-phenanthroline, 14 2-oxocyclohexane-carboxylate, 15 2-aminopyrimidine-4,6-diol, 16 hydrazone, 17 and pyrrolidinylmethylimidazole derivatives 18 have been recently claimed as efficient ligands. Based on the great success achieved in the nitrogen-containing ligands, we envisaged that the compounds having 1,1-diamide motif ( Figure 1) could possibly serve as ligands in the arylation conversion even though their functions as ligands have not been claimed previously.…”