[2] The biosynthesis of marinone begins with 1,3,6,8-tetrahydroxynaphthalene (THN), which is known to be biosynthesized via the condensation of five malonyl-coenzyme A units followed by the aromatization of the resulting pentaketide using a type III polyketide synthase.

[5] Then, 1 undergoes oxidative dearomatization which is catalyzed by VCPO, which is a vanadium-dependent chloroperoxidase enzyme.

Exposure of 5 to mildly basic conditions induces cyclization to yield the α-chloroepoxide, 6.

Next, oxidation at the C-2 position and facile E/Z isomerization of the double bond affords the enone, 8, which undergoes a intramolecular hetero-Diels-Alder to yield debromomarinone.

Lastly, the vanadium-dependent bromoperoxidase catalyzes the bromination of debromomarinone at the C-5 position to result in the formation of marinone.