Reusable Cu₂O-Nanoparticle-Catalyzed Amidation of Aryl Iodides

Abstract

The amidation of aryl iodides using Cu₂O nanoparticles is described. It is a heterogeneous process, no leaching of the Cu₂O species occurs, and the catalyst can be recovered and recycled without loss of activity.

Key words

Cu₂O nanoparticles - heterogeneous catalysis - cross-coupling reaction - amide - aryl iodide

References and Notes

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10

General Procedure for Amidation of Aryl Iodides
Aryl iodide (1 mmol), amide (1.2 mmol), and CuI (10 mol%) were stirred at 120 ˚C in the presence of KOH (1 mmol) in PEG₄₀₀₀ (1 g) under N₂ atmosphere. Progress of the reaction was monitored by TLC. After completion, the reaction flask was cooled to r.t., and the reaction mixture was treated with EtOAc (10 mL). The resulting solution was washed with H₂O (3 × 2 mL). Drying (Na₂SO₄) and evaporation of the solvent gave a residue that was purified on a short pad of silica gel using hexane and EtOAc as eluent. All the isolated products were characterized by IR, ^¹H NMR, and ^¹³C NMR spectroscopy, and elemental analysis. Recyclability Experiment 1-Iodo-4-methylbenzene (5 mmol), benzamide (6 mmol), and CuI (10 mol%) were stirred at 120 ˚C in the presence of KOH (7.5 mmol) in PEG₄₀₀₀ (5 g) under N₂ atmosphere. After the reaction, the reaction material was treated with EtOAc (10 mL) and H₂O (5 mL). The aqueous layer having the Cu₂O nanoparticles were centrifuged, and the precipitate was washed with deionized H₂O (3 ¥ 2 mL) and acetone (3 ¥ 2 mL). After drying in vacuum, the Cu₂O nanoparticles were reused for the fresh reaction of benzamide with 1-iodo-4-methylbenzene.