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- Title
Identification of Cyclopropane Formation in the Biosyntheses of Hormaomycins and Belactosins: Sequential Nitration and Cyclopropanation by Metalloenzymes.
- Authors
Li, Xiaojun; Shimaya, Ryo; Dairi, Tohru; Chang, Wei‐chen; Ogasawara, Yasushi
- Abstract
Hormaomycins and belactosins are peptide natural products that contain unusual cyclopropane moieties. Bioinformatics analysis of the corresponding biosynthetic gene clusters showed that two conserved genes, hrmI/belK and hrmJ/belL, were potential candidates for catalyzing cyclopropanation. Using in vivo and in vitro assays, the functions of HrmI/BelK and HrmJ/BelL were established. HrmI and BelK, which are heme oxygenase‐like dinuclear iron enzymes, catalyze oxidation of the ϵ‐amino group of l‐lysine to afford l‐6‐nitronorleucine. Subsequently, HrmJ and BelL, which are iron‐ and α‐ketoglutarate‐dependent oxygenases, effectively convert l‐6‐nitronorleucine into 3‐(trans‐2‐nitrocyclopropyl)‐alanine through C4−C6 bond installation. These observations disclose a novel pathway of cyclopropane ring construction and exemplify the new chemistry involving metalloenzymes in natural product biosynthesis.
- Subjects
METALLOENZYMES; CYCLOPROPANATION; CYCLOPROPANE; OXYGENASES; BIOSYNTHESIS; PEPTIDES; NITRATION; NATURAL products
- Publication
Angewandte Chemie, 2022, Vol 134, Issue 7, p1
- ISSN
0044-8249
- Publication type
Academic Journal
- DOI
10.1002/ange.202113189