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

Citation:
Murray, LAM, McKinnie SMK, Pepper HP, Erni R, Miles ZD, Cruickshank MC, Lopez-Perez B, Moore BS, George JH.  2018.  Total synthesis establishes the biosynthetic pathway to the naphterpin and marinone natural products. Angewandte Chemie-International Edition. 57:11009-11014.

Date Published:

2018/08

Keywords:

acid 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.

Notes:

n/a

Website

DOI:

10.1002/anie.201804351