Mechanochemical synthesis using hypervalent iodine reagents

Mechanochemical activation offers a powerful means of expanding the reactivity of hypervalent iodine reagents while advancing solvent-free synthetic methodologies. This review surveys the evolution of iodine(III) and iodine(V) chemistry in the solid state, from foundational solvent-free oxidations to mechanochemical approaches that enable efficient heterocycle construction, C–H functionalization, cascade dioxygenation, fluoroiodane-mediated fluorocyclization, and redox-initiated polymerization. Mechanical energy alters aggregation, enhances reagent–substrate contact, and promotes transformation pathways not readily accessible in solution. These developments showcase the distinctive advantages of mechanochemical hypervalent iodine chemistry and its growing impact on sustainable synthetic methodology development.