An efficient, green and first catalytic process has been developed for the direct synthesis of amides from readily available petroleum by‐products (methylarenes) and amines using an iron catalyst. In this new catalytic reaction, the methyl group of the methylarene is oxidized to the corresponding aldehyde through non‐directed C H oxidation followed by its oxidative amidation with N‐chloroamine, yielding the carboxylic amide. Oxidation with an iron catalyst, tert‐butyl hydroperoxide (TBHP) as sole oxidant, the synthesis of amides under mild reaction conditions and the utilization of methylarenes as starting material make this methodology novel and environmentally benign.
A direct oxidative amidation between methylarenes and aqueous ammonia using a tert‐butyl hydroperoxide and tetrabutylammonium iodide (TBHP/TBAI) oxidation system with co‐catalysis of iron(III) chloride has been developed. Both coupling partners were used in their native form to render prior functionalization unnecessary and afford a facile approach to aromatic primary amides.