An efficient synthesis of methyl nicotinates/6-halonicotinates by the domino isomerization of 4-propargyl/(3-halopropargyl)-5-methoxyisoxazoles under Fe(II)/Au(I) relay catalysis was developed. It was found that FeNTf₂ is an effective catalyst for first step of the domino isomerization, transformation of isoxazole to 2H-azirine, which is compatible with Ph₃PAuNTf₂, catalyzing the second step.