A solvent-free approach that involves microwave (MW) exposure of neat reactants (undiluted) catalyzed by the surfaces of less-expensive and recyclable mineral Supports such Lis alumina, silica, clay, or 'doped' surfaces is presented which is applicable to a wide range of cleavage, condensation, cyclization, rearrangement, oxidation and reduction reactions including rapid one-pot assembly of heterocyclic compounds from in situ generated reactive intermediates. The strategy is adaptable to multi-component reactions e.g. Ugi and Biginelli reactions for rapid assembly of a library Of compounds. Synthesis of a wide variety of. significant precursors and intermediates namely, enones, imines, enamines, nitroalkenes, and oxidized Sulfur species is possible and their value in concise MW synthesis of 2-aroylbenzofurans, and thiazole derivatives is illustrated. Ultrasound- and MW-assisted solventless preparation of ionic liquids and their application in alkylation and metal -catalyzed multi-component reactions is described. Efficient reaction of epoxides with carbon dioxide provides ready access to cyclic carbonates using only a catalytic amount of recyclable indium-based ionic liquid. MW heating in aqueous reaction media enables expeditious N-alkylation reactions of amines and hydrazines to afford a series of heterocyclic ring systems such as N-azacycloalkanes, 4,5-dihydropyrazoles, pyrazolidines etc.