CH bond arylation of anilides inside copper-exchanged zeolites

• The first meta-selective CH bond arylation of anilides inside copper-exchanged zeolites is presented.
• DFT studies indicate the well-fitted copper-aryl complexes inside zeolite frameworks.
• Electron micrographs, elemental analyses, and reusability study show no observable metal cluster formations or leaching of catalytically active copper species.
• The practical synthetic potential of copper-exchanged zeolites as promising supported molecular catalysts is demonstrated.

Syntheses of fine-chemicals using heterogeneous catalysts have tremendous industrial potentials, yet CH functionalization studies have been largely focused on homogeneous catalysis. We report here the first meta-selective CH bond arylation of anilides inside copper-exchanged zeolites. Mid- or large-pore zeolite frameworks are selected as supports to access large organic molecules, and atomically distributed copper catalysts exhibit high activities (84–90% conversions) toward direct arylation of anilides with diphenyliodonium salt on 0.5 mol% copper concentration. Computational studies indicate the well-fitted copper-aryl complexes inside zeolite frameworks. Electron micrographs, elemental analyses, and reusability study show no observable leaching of catalytically active copper species during the reactions tested. These results demonstrate the practical synthetic potential of copper-exchanged zeolites as promising supported molecular catalysts to afford biaryl motifs-containing compounds with high catalytic activity, chemical stability, and recyclability.

Copper-aryl complexes inside the zeolite frameworks are meta-selective and give products in high yields even at 0.5 mol% copper loading.Figure optionsDownload high-quality image (173 K)Download as PowerPoint slide