氮丙啶
化学
羟基化
反应性(心理学)
戒指(化学)
酶
生物信息学
组合化学
部分
胺气处理
区域选择性
立体化学
生物化学
催化作用
有机化学
医学
替代医学
病理
基因
作者
Lide Cha,Jared C. Paris,Brady Zanella,Martha Spletzer,Angela Yao,Yisong Guo,Wei‐chen Chang
摘要
Aziridines are compounds with a nitrogen-containing three-membered ring. When it is incorporated into natural products, the reactivity of the strained ring often drives the biological activities of aziridines. Despite its importance, the enzymes and biosynthetic strategies deployed to install this reactive moiety remain understudied. Herein, we report the use of in silico methods to identify enzymes with potential aziridine-installing (aziridinase) functionality. To validate candidates, we reconstitute enzymatic activity in vitro and demonstrate that an iron(IV)-oxo species initiates aziridine ring closure by the C–H bond cleavage. Furthermore, we divert the reaction pathway from aziridination to hydroxylation using mechanistic probes. This observation, isotope tracing experiments using H218O and 18O2, and quantitative product analysis, provide evidence for the polar capture of a carbocation species by the amine in the pathway to aziridine installation.
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