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An efficient methodology has been developed for C−N cross‐coupling reaction between aryl halide and amine using a catalytic system comprised of CuI and N,N‐dimethyl amino pyridine (DMAP). Coupling reactions were carried out in DMSO at 120 °C in presence of 5 mol% CuI, 20 mol% DMAP and 2.5 equivalent of KOH. Addition of DMAP was found to be beneficial in accelerating the rate of reaction significantly. Both aryl iodides and aryl bromides could be successfully coupled with different primary and secondary amines to furnish the desired cross‐coupling product in high yield. A copper complex [Cu(DMAP)4I]I made by combining CuI and DMAP was found to produce superior result for the Buchwlad‐Hartwig cross coupling reaction. The use of 2 mol% of the copper complex is sufficient to produce high yield of the product.

and 13 C spectra were recorded in Bruker Avance 300 MHz instrument. Chemical shifts are given in δ units relative to the tetramethylsilane (TMS) signal as an internal reference in CDCl 3 . Coupling constants (J) are reported in hertz (Hz). IR spectra were recorded in Perkin -Elmer Spectrum RXI FT-IR spectrometer. Silica gel (230-400 mesh) was used for column chromatography.

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