Premium
Nucleophilic Reactivity of a Copper(II)–Superoxide Complex
Author(s) -
Pirovano Paolo,
Magherusan Adriana M.,
McGlynn Ciara,
Ure Andrew,
Lynes Amy,
McDonald Aidan R.
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201311152
Subject(s) - chemistry , pterin , nucleophile , superoxide , electrophile , reactivity (psychology) , nucleophilic addition , medicinal chemistry , stereochemistry , organic chemistry , enzyme , catalysis , cofactor , medicine , alternative medicine , pathology
Abstract Metal‐bound superoxide intermediates are often implicated as electrophilic oxidants in dioxygen‐activating metalloenzymes. In the nonheme iron α‐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 α‐ketoglutarate dependent and pterin‐dependent enzymes.