Fungal Sulfotransferase from <i>Metarhizium majus</i> Catalyzes the Formation of <i>PPZ</i> Pathway Intermediate Peramine-8‑<i>O</i>‑sulfate

PpzF, a sulfotransferase encoded in the PPZ biosynthetic gene cluster from the fungal insect pathogen Metarhizium majus, was shown to catalyze the formation of peramine-8-O-sulfate from 8-hydroxyperamine. Both the substrate and the product were detected in Penicillium paxilli expressing ppzA–ppzG, supporting their roles as pathway intermediates. Gene ppzF is the second fungal sulfotransferase gene to be functionally characterized and the first whose endogenous role has been revealed. The discovery of peramine-8-O-sulfate represents a significant step toward identifying the elusive final product(s) of the PPZ pathway.