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- Title
Pathway from N‐Alkylglycine to Alkylisonitrile Catalyzed by Iron(II) and 2‐Oxoglutarate‐Dependent Oxygenases.
- Authors
Chen, Tzu‐Yu; Chen, Jinfeng; Tang, Yijie; Zhou, Jiahai; Guo, Yisong; Chang, Wei‐chen
- Abstract
N‐alkylisonitrile, a precursor to isonitrile‐containing lipopeptides, is biosynthesized by decarboxylation‐assisted ‐N≡C group (isonitrile) formation by using N‐alkylglycine as the substrate. This reaction is catalyzed by iron(II) and 2‐oxoglutarate (Fe/2OG) dependent enzymes. Distinct from typical oxygenation or halogenation reactions catalyzed by this class of enzymes, installation of the isonitrile group represents a novel reaction type for Fe/2OG enzymes that involves a four‐electron oxidative process. Reported here is a plausible mechanism of three Fe/2OG enzymes, Sav607, ScoE and SfaA, which catalyze isonitrile formation. The X‐ray structures of iron‐loaded ScoE in complex with its substrate and the intermediate, along with biochemical and biophysical data reveal that ‐N≡C bond formation involves two cycles of Fe/2OG enzyme catalysis. The reaction starts with an FeIV‐oxo‐catalyzed hydroxylation. It is likely followed by decarboxylation‐assisted desaturation to complete isonitrile installation.
- Subjects
OXYGENASES; IRON; HALOGENATION; ENZYMES; HYDROXYLATION; ENZYME kinetics
- Publication
Angewandte Chemie, 2020, Vol 132, Issue 19, p7437
- ISSN
0044-8249
- Publication type
Academic Journal
- DOI
10.1002/ange.201914896