|Title||Total synthesis establishes the biosynthetic pathway to the naphterpin and marinone natural products|
|Publication Type||Journal Article|
|Year of Publication||2018|
|Authors||Murray L.AM, McKinnie S.MK, Pepper H.P, Erni R., Miles Z.D, Cruickshank M.C, Lopez-Perez B., Moore BS, George J.H|
|Type of Article||Article|
|Keywords||acid biosynthesis; antibiotics; biomimetic synthesis; biosynthesis; chemistry; dearomatization; merochlorins; Meroterpenoids; microorganisms; naphthoquinones; rearrangement; sp; Streptomyces; structural elucidation; total synthesis; vanadium-dependent chloroperoxidases|
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.