Mechanistic Investigation of a Non-Heme Iron Enzyme Catalyzed Epoxidation in (-)-4'-Methoxycyclopenin Biosynthesis.
J Am Chem Soc
; 138(33): 10390-3, 2016 08 24.
Article
em En
| MEDLINE
| ID: mdl-27442345
ABSTRACT
Mechanisms have been proposed for α-KG-dependent non-heme iron enzyme catalyzed oxygen atom insertion into an olefinic moiety in various natural products, but they have not been examined in detail. Using a combination of methods including transient kinetics, Mössbauer spectroscopy, and mass spectrometry, we demonstrate that AsqJ-catalyzed (-)-4'-methoxycyclopenin formation uses a high-spin Fe(IV)-oxo intermediate to carry out epoxidation. Furthermore, product analysis on (16)O/(18)O isotope incorporation from the reactions using the native substrate, 4'-methoxydehydrocyclopeptin, and a mechanistic probe, dehydrocyclopeptin, reveals evidence supporting oxoâhydroxo tautomerism of the Fe(IV)-oxo species in the non-heme iron enzyme catalysis.
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Base de dados:
MEDLINE
Assunto principal:
Enzimas
/
Compostos de Epóxi
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Biocatálise
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Ferro
Idioma:
En
Ano de publicação:
2016
Tipo de documento:
Article