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Total Synthesis Establishes the Biosynthetic Pathway to the Naphterpin and Marinone Natural Products
Author(s) -
Murray Lauren A. M.,
McKinnie Shaun M. K.,
Pepper Henry P.,
Erni Reto,
Miles Zachary D.,
Cruickshank Michelle C.,
LópezPérez Borja,
Moore Bradley S.,
George Jonathan H.
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201804351
Subject(s) - chemistry , biosynthesis , halogenation , total synthesis , stereochemistry , biomimetic synthesis , enzyme , chlorine , biochemistry , organic chemistry
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.