A series of 12 silica gel-bound enaminones and their Cu(II) complexes were prepared and tested for their suitability as heterogeneous catalysts in azomethine imine-alkyne cycloadditions (CuAIAC). Immobilized Cu(II)-enaminone complexes showed promising catalytic activity in the CuAIAC reaction, but these new catalysts suffered from poor reusability. This was not due to the decoordination of copper ions, as the use of enaminone ligands with additional complexation sites resulted in negligible improvement. On the other hand, reusability was improved by the use of 4-aminobenzoic acid linker, attached to 3-aminopropyl silica gel via an amide bond to the enaminone over the more hydrolytically stable N-arylenamine C-N bond. The study showed that silica gel-bound Cu(II)-enaminone complexes are readily available and suitable heterogeneous catalysts for the synthesis of 6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazoles.
Keywords: 1,3-dipolar cycloadditions; 2,3-dihydropyrazolo[1,2-a]pyrazoles; azomethine imines; copper-catalyzed azomethine imine-alkyne cycloaddition (CuAIAC); ynones.