Leveraging vanadium and H2O2 as green oxidant in functionalisation of organic molecules

Vanadium catalysts paired with hydrogen peroxide (H₂O₂) as a green oxidant offer a versatile and sustainable platform for the selective oxidative functionalization of organic molecules. This review provides a comprehensive survey of recent advances in vanadium–H₂O₂ catalysis across essential transformations, namely epoxidation, oxidative cleavage of CC bonds, oxidation of alcohol, C–H bond activation, sulfide oxidation, halogenation, and tandem oxidative processes. Emphasis is placed on how ligand design particularly Schiff base ligands and polyoxometalates tunes catalytic activity, selectivity, and stability. The role of reactive vanadium species, such as mono- and peroxovanadates along with mechanistic insights, structure–activity relationships, and the influence of solvent and oxidant control are discussed. Sustainability is evaluated using green chemistry metrics including atom economy, E-factor, process mass intensity (PMI), turnover number (TON), and turnover frequency (TOF). Despite notable progress, challenges such as catalyst deactivation, limited efficacy in unactivated C–H oxidations, and insufficient mechanistic resolution persist. This review concludes by highlighting emerging strategies in ligand design and reactor engineering, positioning vanadium–H₂O₂ systems as promising platforms for scalable, efficient, and sustainable oxidation chemistry.