Abstract: Functionalized asymmetric porphyrins bearing highly reactive centers in substituents at the mesopositions were synthesized in good yields by the reaction of 5,15-diphenylporphyrin with organolithium reagents. Using these porphyrins as precursors highly complex tetrapyrrolic systems are accessible. The synthetic strategy is based on our earlier reports on the combined use of organolithium and alkyliodide reagents for the functionalization of porphyrins.