Selective Ortho-Hydroxylation-Defluormation of 2-FIuoi ophenolates with a Bis(n-oxo)dicopper(III) Species

摘要

The bis(μ-oxo)dicopper(III) species [Cu~(III)2(μ-O)2(m-XYL~(MeAN))~(2+) (1) promotes the electrophilic ortho-hydroxylation-defluorination of 2-fluorophenolates to give the corresponding catechols, a reaction that is not accomplishable with a (η~2:η~2-O2)dicopper(U) complex. Isotopic labeling studies show that the incoming oxygen atom originates from the bis(pi-oxo) unit. Ortho-hydroxylation-defluorination occurs selectively in intramolecular competition with other ortho-substituents such as chlorine or bromine.