Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 53, Issue 23, Pages 5946-5950Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201311152
Keywords
bioinorganic chemistry; dioxygen activation; nucleophilic reactivity; reaction mechanisms; superoxide complexes
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Funding
- European Union [FP7-333948]
- Science Foundation Ireland (SFI) [SFI/12/RC/2278]
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Metal-bound superoxide intermediates are often implicated as electrophilic oxidants in dioxygen-activating metalloenzymes. In the nonheme iron alpha-ketoglutarate dependent oxygenases and pterin-dependent hydroxylases, however, Fe-III-superoxide intermediates are postulated to react by nucleophilic attack on electrophilic carbon atoms. By reacting a Cu-II-superoxide complex (1) with acyl chloride substrates, we have found that a metal-superoxide complex can be a very reactive nucleophile. Furthermore, 1 was found to be an efficient nucleophilic deformylating reagent, capable of Baeyer-Villiger oxidation of a number of aldehyde substrates. The observed nucleophilic chemistry represents a new domain for metal-superoxide reactivity. Our observations provide support for the postulated role of metal-superoxide intermediates in nonheme iron alpha-ketoglutarate dependent and pterin-dependent enzymes.
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