全合成确立了萘菲啶和马琳酮天然产物的生物合成途径。
Total Synthesis Establishes the Biosynthetic Pathway to the Naphterpin and Marinone Natural Products.
机构信息
Department of Chemistry, University of Adelaide, Adelaide, SA, 5005, Australia.
Center for Marine Biotechnology and Biomedicine, Scripps Institution of Oceanograph, University of California, San Diego, La Jolla, CA, 92093, USA.
出版信息
Angew Chem Int Ed Engl. 2018 Aug 20;57(34):11009-11014. doi: 10.1002/anie.201804351. Epub 2018 Jul 23.
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.
摘要
萘醌类和马琳酮是一种独特的芳香氧化模式的萘醌单萜，由 1,3,6,8-四羟基萘（THN）生物合成。我们提出，尽管这些天然产物中没有氯，但钒依赖的氯化过氧化物酶（VCPO）酶对 THN 衍生物的隐匿性卤化是这一生物合成途径的关键。这一推测激发了一种全合成方法来模拟萘醌/马琳酮的生物合成途径。在验证这一生物发生假说时，发现了两种 VCPO，它们可以相互转化几种提议的生物合成中间体。
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