Methyl 4-aminopyrrole-2-carboxylates were synthesized in one-pot mode by the relay catalytic cascade reaction of 5-methoxyisoxazoles with pyridinium ylides by the use of a FeCl2/Et3N binary catalytic system leading to 1-(5-methoxycarbonyl-1H-pyrrol-3-yl)pyridinium salts followed by hydrazinolysis. The approach permits the introduction of a substituent at the pyrrole nitrogen via a nucleophilic reaction of the pyrrolylpyridinium ylide derived from the salt. Catalytic reduction of the ylides gives methyl 4-piperidinopyrrole-2-carboxylates.