An iron porphyrin-catalyzed three-component reaction of ethyl diazoacetate with aliphatic amines and 尾,纬-unsaturated 伪-keto esters is reported. The use of iron porphyrin catalyst allows aliphatic amines to be used as the substrate without encountering catalyst poisoning issue and a series of 尾-hydroxy-伪-amino esters are produced in high yields with excellent regioselectivities.