Protonation of the reactive intermediate produced in the reaction between trimethyl phosphite and dimethyl acetylenedicarboxylate or diethyl acetylenedicarboxylate by resorcinol, 5- methylresorcinol, 2,5-dihydroxyacetophenone, 4-chloro-2-methylphenol, 4-chloro-3,5-dimethylphenol, 4-hydroxypyridine, 2-hydroxypyridine, 3-hydroxypyridine, or 8-hydroxyquinoline leads to vinylphosphonium salts, which undergo Michael addition with the conjugate base of the OH-acid to produce highly functionalized 2-oxo-2H-chromene or azacoumarins in good yields.