An iron porphyrin-catalyzed three-component reaction of ethyl diazoacetate with aliphatic amines and β,γ-unsaturated α-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 β-hydroxy-α-amino esters are produced in high yields with excellent regioselectivities.