Three-component coupling of carbonyl compounds, homoallylic alcohols, and nitriles has been achieved using 20mol% of phosphomolybdic acid (PMA) at ambient temperature via the Prins–Ritter sequence to furnish 4-amidotetrahydropyrans in high yields with all cis selectivity. Spirocyclic-4-amidotetrahydropyrans are obtained using cyclic ketones.