Heterologous biosynthesis of elsinochrome A sheds light on the formation of the photosensitive perylenequinone system

Chemical Science
Jinyu HuYit-Heng Chooi

Abstract

Perylenequinones are a class of aromatic polyketides characterised by a highly conjugated pentacyclic core, which confers them with potent light-induced bioactivities and unique photophysical properties. Despite the biosynthetic gene clusters for the perylenequinones elsinochrome A (1), cercosporin (4) and hypocrellin A (6) being recently identified, key biosynthetic aspects remain elusive. Here, we first expressed the intact elc gene cluster encoding 1 from the wheat pathogen Parastagonospora nodorum heterologously in Aspergillus nidulans on a yeast-fungal artificial chromosome (YFAC). This led to the identification of a novel flavin-dependent monooxygenase, ElcH, responsible for oxidative enolate coupling of a perylenequinone intermediate to the hexacyclic dihydrobenzo(ghi)perylenequinone in 1. In the absence of ElcH, the perylenequione intermediate formed a hexacyclic cyclohepta(ghi)perylenequinone system via an intramolecular aldol reaction resulting in 6 and a novel hypocrellin 12 with opposite helicity to 1. Theoretical calculations supported that 6 and 12 resulted from atropisomerisation upon formation of the 7-membered ring. Using a bottom-up pathway reconstruction approach on a tripartite YFAC system developed in this ...Continue Reading

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Citations

Mar 15, 2019·Natural Product Reports·Robert A Hill, Andrew Sutherland
May 3, 2019·Angewandte Chemie·Sebastian ObermaierMichael Müller
Jul 16, 2019·Fungal biology and biotechnology·Andrew S UrquhartAlexander Idnurm
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Nov 17, 2020·Natural Product Reports·Wolfgang Hüttel, Michael Müller
Jan 7, 2021·Natural Product Reports·Jiawang LiuYoucai Hu
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Aug 14, 2020·Journal of Natural Products·Zeinab Y Al SubehNicholas H Oberlies
Jan 26, 2022·The Journal of Organic Chemistry·Zeinab Y Al SubehShabnam Hematian

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Methods Mentioned

BETA
NMR

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