[3] 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.

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

Compound 2 then undergoes two consecutive chlorinations at the C2 position, catalyzed by VCPO, to yield 4.

Next, a VCPO catalyzed α-hydroxyketone rearrangement shifts the geranyl substituent from C-4 to C-3, yielding 5.

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.