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Synlett 2015; 26(15): 2060-2066
DOI: 10.1055/s-0034-1381023
DOI: 10.1055/s-0034-1381023
synpacts
Nucleophilic Reactivity of a Metal-Bound Superoxide Ligand
Further Information
Publication History
Received: 29 April 2015
Accepted after revision: 03 June 2015
Publication Date:
16 July 2015 (online)
Abstract
Metal–superoxide species have frequently been implicated as transient intermediates in dioxygen activating metalloenzymes. The metal-bound superoxide moiety has been proposed to react both as an electrophile and a nucleophile. In general, model complexes that mimic metalloenzyme function have been shown to react as electrophiles, and none have displayed nucleophilic reactivity. Herein, we highlight a recent contribution from our group in which we demonstrated the first well-defined example of a metal–superoxide acting as a nucleophile. We have shown the propensity for a copper-superoxide species to perform nucleophilic deformylation of various aldehydes. In doing so, we have provided experimental support for the postulated role of an iron(III)–superoxide reacting as a nucleophile in the α-ketoglutarate-dependent dioxygenases amongst others.
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