Nucleophilic Reactivity of a Copper(II)-Superoxide Complex

摘要

Metal-bound superoxide intermediates are often implicated as electrophilic oxidants in dioxygen-activating metalloenzym.es. In the nonheme iron a-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-super oxide 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 a-ketoglutarate dependent and pterin-dependent enzymes.