Direct α-arylation of ketones efficiently catalyzed by Cu-MOF-74

Abstract

The activity and reusability of Cu-MOF-74 as heterogeneous catalyst were studied in the Cu-catalyzed CeC crosscoupling reaction of 4-iodotoluene (4-IT) with acetylacetone (AcAc) to direct synthesis of α-aryl-ketones. CuMOF-74 is characterized by having unsaturated copper sites into its highly porous metal-organic framework that can play a crucial role in catalytic applications. The influence of critical reaction variables such as solvent, reaction temperature, AcAc/4-IT ratio, catalyst concentration and basic agent (type and concentration) were evaluated. High conversions were achieved at 140°C, 5mol % of catalyst, AcAc/4-IT ratio of 2:1, DMF as solvent and 1.5 equivalent of Cs2CO3 base. The C-arylation between 4-IT and AcAc proceeded only in the presence of CuMOF-74 material, being very low the transformation in absence of the solid catalyst. Cu-MOF-74 material displayed a remarkable structural stability, regarding its XRD patterns and solid recovery degree after several reaction cycles, which was also complemented by the negligible amount of copper leached in the reaction media. This catalyst showed promising results in comparison to other homogeneous and heterogeneous Cu-based catalysts. This work evidences the great potential of MOF materials as heterogeneous catalysts in fine chemistry applications.