3,5-Disubstituted isoxazoles and isoxazolines undergo an iron-catalyzed reductive ring-opening in aged N-methyl-2-pyrrolidone (NMP). 5-Hydroxy-N-methyl-2-pyrrolidone generated in situ via a simple activation of commercial NMP acts as the hydrogen donor in the iron-catalyzed transfer hydrogenation reaction. It is the first example employing a combination of an iron catalyst and 5-hydroxy-N-methyl-2-pyrrolidone as reducing agents in a transfer hydrogenation reaction. The protocol is highly efficient for the synthesis of β-enaminones and 1,3-diketones, providing a versatile route for the preparation of these 1,3-difunctional compounds bearing diversified substitution patterns.