在工程化金核菌素途径中，一种非典型 CYP 介导的四电子氧化-环化级联反应导致吡喃的形成。
Pyran formation by an atypical CYP-mediated four-electron oxygenation-cyclization cascade in an engineered aureothin pathway.
机构信息
Dept. Biomolecular Chemistry, Leibniz Institute for Natural Product Research and Infection Biology, HKI, Beutenbergstrasse 11a, 07745 Jena, Germany.
出版信息
Chembiochem. 2012 Oct 15;13(15):2196-9. doi: 10.1002/cbic.201200406. Epub 2012 Sep 7.
Abstract
Small changes, big effect: A new aureothin derivative, aureopyran, which features an unusual pyran backbone, was generated by simply altering the enzymatic methylation topology. The α-pyrone ring hampers the correct placement of the polyketide backbone in the multifunctional cytochrome P450 monooxygenase AurH. Instead of a tetrahydrofuran ring, an oxo intermediate is formed that readily undergoes a rare electrocyclization reaction.
摘要
微小的变化，巨大的影响：通过简单改变酶促甲基化拓扑结构，生成了一种新型金蝶素衍生物——金蝶吡喃，其具有不寻常的吡喃骨架。α-吡喃酮环阻碍了多酮骨架在多功能细胞色素 P450 单加氧酶 AurH 中的正确定位。形成的不是四氢呋喃环，而是一个氧中间物，它很容易发生罕见的电环化反应。
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