A new protocol for the N‐arylation of aryl halides with anilines using Cu nanoparticles in polyethylene glycol (PEG) as an efficient and reusable catalytic system has been developed. The reaction did not require any cocatalyst. Various solvents were screened, and PEG400 provided the best results. The studies showed that the mechanism of catalytic action is dependent on the size of the nanoparticles. The Cu nanoparticles and PEG were recyclable and retained their activity. This newly developed protocol was also found to be suitable for the cross coupling of NH heterocycles with iodobenzene. The present methodology offers several advantages, such as excellent yields, short reaction times, and milder reaction conditions.

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Ceric ammonium nitrate (CAN) efficiently catalysed the synthesis of benzimidazole derivatives from o-phenylenediamine and aldehydes in PEG. This method provides a novel route for the synthesis of benzimidazoles in good yields with little catalyst loading. The recovery and the successful reutilization of the solvent system are also presented. Moreover, the easy set-up and purification tasks of this sustainable method make it appealing for bulk industry applications.

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A novel strategy to effect the Markovnikov addition between azoles and vinyl-acetate is described. The main attractive features of this process are a mild base catalyst, recyclability of solvent PEG, excellent yields of products, and easy workup procedure.