A variety of substituted quinoline/pyridine, thiochromene and naphthalene derivatives, which might be of biological and medicinal value, were synthesized by copper-catalyzed domino SN2′/coupling, SN2′/deacylation/coupling and SN2′/coupling/elimination reactions. The method provides a general and convenient approach to the synthesis of various substituted cyclic compounds from the corresponding Baylis-Hillman (B-H) acetates and N-/S-/C-nucleophiles.