Total synthesis establishes the biosynthetic pathway to the naphterpin and marinone natural products

TitleTotal synthesis establishes the biosynthetic pathway to the naphterpin and marinone natural products
Publication TypeJournal Article
Year of Publication2018
AuthorsMurray L.AM, McKinnie S.MK, Pepper H.P, Erni R., Miles Z.D, Cruickshank M.C, Lopez-Perez B., Moore BS, George J.H
Volume57
Pagination11009-11014
Date Published2018/08
Type of ArticleArticle
ISBN Number1433-7851
Accession NumberWOS:000442863700038
Keywordsacid biosynthesis; antibiotics; biomimetic synthesis; biosynthesis; chemistry; dearomatization; merochlorins; Meroterpenoids; microorganisms; naphthoquinones; rearrangement; sp; Streptomyces; structural elucidation; total synthesis; vanadium-dependent chloroperoxidases
Abstract

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.

DOI10.1002/anie.201804351
Student Publication: 
No
Research Topics: