Substrate-Triggered Formation of a Peroxo-Fe2(III/III) Intermediate during Fatty Acid Decarboxylation by UndA

Zhang, Bo; Rajakovich, Lauren J.; Van Cura, Devon; Blaesi, Elizabeth J.; Mitchell, Andrew J.; Tysoe, Christina R.; Zhu, Xuejun; Streit, Bennett R.; Rui, Zhe; Zhang, Wenjun; Boal, Amie K.; Krebs, Carsten; Bollinger, J. Martin

doi:10.1021/jacs.9b06093

Title: Substrate-Triggered Formation of a Peroxo-Fe₂(III/III) Intermediate during Fatty Acid Decarboxylation by UndA

Journal Article · Thu Sep 05 04:00:00 UTC 2019 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.9b06093 · OSTI ID:1569873

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Pennsylvania State Univ., University Park, PA (United States)
Univ. of California, Berkeley, CA (United States)

The iron-dependent oxidase UndA cleaves one C3–H bond and the C1–C2 bond of dodecanoic acid to produce 1-undecene and CO₂. A published X-ray crystal structure showed that UndA has a heme-oxygenase-like fold, thus associating it with a structural superfamily that includes known and postulated non-heme diiron proteins, but revealed only a single iron ion in the active site. Mechanisms proposed for initiation of decarboxylation by cleavage of the C3–H bond using a monoiron cofactor to activate O₂ necessarily invoked unusual or potentially unfeasible steps. Here we present spectroscopic, crystallographic, and biochemical evidence that the cofactor of Pseudomonas fluorescens Pf-5 UndA is actually a diiron cluster and show that binding of the substrate triggers rapid addition of O₂ to the Fe₂(II/II) cofactor to produce a transient peroxo-Fe₂(III/III) intermediate. Finally, the observations of a diiron cofactor and substrate-triggered formation of a peroxo-Fe₂(III/III) intermediate suggest a small set of possible mechanisms for O₂, C3–H and C1–C2 activation by UndA; these routes obviate the problematic steps of the earlier hypotheses that invoked a single iron.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC02-76SF00515; AC02-06CH11357

OSTI ID:: 1569873

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 37 Vol. 141; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: ENGLISH

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
absorption
cluster chemistry
diirons
organic reactions
oxidation

Title: Substrate-Triggered Formation of a Peroxo-Fe2(III/III) Intermediate during Fatty Acid Decarboxylation by UndA

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Title: Substrate-Triggered Formation of a Peroxo-Fe₂(III/III) Intermediate during Fatty Acid Decarboxylation by UndA