Supported Pd-Catalyzed Carbonylative Transformation of Biomass-Derived Furfural to 2,5-Furandicarboxylic Acid

Abstract

Herein, we have developed an unprecedented route for the synthesis of 2,5-furandicarboxylic acid (FDCA) i.e. monomer of polyethylene furanoate (PEF) polymer from biomass-derived furfural. The developed protocol exhibits a sequential bromination, carbonylative esterification and oxidative hydrolysis from C-5 based renewable furfural to C-6 based FDCA synthesis. Firstly, the unstable furfural efficiently transformed into 5-bromofuran-2-carbaldehyde under a simple reagent system. Next, the developed polystyrene-supported palladium (Pd@PS) nanoparticles (NPs) catalyzed carbonylative esterification of 5-bromofuran-2-carbaldehyde to various alkyl 5-formylfuran-2-carboxylates using oxalic acid as CO source and alcohols as a nucleophile is the key step associated in the present methodology. Additionally, Pd@PS NPs efficiently catalyzed the oxidative hydrolysis of alkyl 5-formylfuran-2-carboxylates to FDCA in good yield, under milder reaction conditions.