Biosynthesis of Viridicatol in <em>Penicillium palitans</em> Implies a Cytochrome P450-Mediated <em>meta</em> Hydroxylation at a Monoalkylated Benzene Ring
Org Lett. 2021 Dec 20. doi: 10.1021/acs.orglett.1c03932. Online ahead of print.
Cyclopenol (1) and viridicatol (6) with m-hydroxyl groups were isolated from a culture of Penicillium palitans. Genome mining and heterologous expression in Aspergillus nidulans led to the identification of their biosynthetic gene cluster and the cytochrome P450 enzyme VdoD responsible for the meta hydroxylation. Precursor feeding experiments into vdoD transformant proved the conversion of cyclopenin (2) to 1, which then undergoes a spontaneous or VdoA-catalyzed rearrangement to 6. A direct conversion of viridicatin (5) to 6 by VdoD was not detected.