Heterologous expression of the flavipucine biosynthetic gene cluster in Aspergillus nidulans led to the production of flavipucine (1) and dihydroisoflavipucine (3), as well as six unusual flavipucine related products containing three classes of heterocycles. This combined with gene inactivation, chemical complementation, and transcriptome analysis demonstrated unprecedented ways to form 2-pyridone and 2-pyrone structures by the oxidative rearrangements of pyrrolinone precursors as well as provided insights into the biosynthesis of this important class of natural products.