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Selective ortho-hydroxylation-defluorination of 2-fluorophenolates with a bis(μ-oxo)dicopper(III) species
Joan Serrano-Plana1, Isaac Garcia-Bosch, Ryosuke Miyake
1Grup de Química Bioinorgànica i Supramolecular (QBIS), Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona (Catalonia) (Spain).
Abstract:
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(II) complex. Isotopic labeling studies show that the incoming oxygen atom originates from the bis(μ-oxo) unit. Ortho-hydroxylation-defluorination occurs selectively in intramolecular competition with other ortho-substituents such as chlorine or bromine.
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