期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 138, 期 33, 页码 10390-10393出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b05400
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资金
- North Carolina State University
- Carnegie Mellon University
- NIH
- NIH Office of the Director
- National Institute of Neurological Disorders and Stroke [R21 NS089893]
Mechanisms have been proposed for alpha-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, Mossbauer 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 O-16/O-18 isotope incorporation from the reactions using the native substrate, 4'-methoxydehydrocyclopeptin, and a mechanistic probe, dehydrocyclopeptin, reveals evidence supporting oxo <-> hydroxo tautomerism of the Fe(IV)-oxo species in the non-heme iron enzyme catalysis.
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