Total Synthesis Establishes the Biosynthetic Pathway to the Naphterpin and Marinone Natural Products.
Lauren A M MurrayShaun M K McKinnieHenry P PepperReto ErniZachary D MilesMichelle C CruickshankBorja López-PérezBradley S MooreJonathan H GeorgePublished in: Angewandte Chemie (International ed. in English) (2018)
The naphterpins and marinones are naphthoquinone meroterpenoids with an unusual aromatic oxidation pattern that is biosynthesized from 1,3,6,8-tetrahydroxynaphthalene (THN). We propose that cryptic halogenation of THN derivatives by vanadium-dependent chloroperoxidase (VCPO) enzymes is key to this biosynthetic pathway, despite the absence of chlorine in these natural products. This speculation inspired a total synthesis to mimic the naphterpin/marinone biosynthetic pathway. In validation of this biogenetic hypothesis, two VCPOs were discovered that interconvert several of the proposed biosynthetic intermediates.