Selective Ortho-Hydroxylation–Defluorination of 2-Fluorophenolates with a Bis(μ-oxo)dicopper(III) Species†
Joan Serrano-Plana
Grup 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)
Search for more papers by this authorDr. Isaac Garcia-Bosch
Grup 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)
Department of Chemistry, The Johns Hopkins University, Baltimore, MD 21218 (USA)
Search for more papers by this authorDr. Ryosuke Miyake
Department of Chemistry and Biochemistry, Graduate School of Humanities and Sciences, Ochanomizu University, 2-1-1 Otsuka, Bunkyo-Ku, Tokyo 112-8610 (Japan)
Search for more papers by this authorCorresponding Author
Dr. Miquel Costas
Grup 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)
Grup 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)Search for more papers by this authorCorresponding Author
Dr. Anna Company
Grup 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)
Grup 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)Search for more papers by this authorJoan Serrano-Plana
Grup 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)
Search for more papers by this authorDr. Isaac Garcia-Bosch
Grup 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)
Department of Chemistry, The Johns Hopkins University, Baltimore, MD 21218 (USA)
Search for more papers by this authorDr. Ryosuke Miyake
Department of Chemistry and Biochemistry, Graduate School of Humanities and Sciences, Ochanomizu University, 2-1-1 Otsuka, Bunkyo-Ku, Tokyo 112-8610 (Japan)
Search for more papers by this authorCorresponding Author
Dr. Miquel Costas
Grup 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)
Grup 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)Search for more papers by this authorCorresponding Author
Dr. Anna Company
Grup 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)
Grup 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)Search for more papers by this authorFinancial support for this work was provided by the European Commission (FP7-PEOPLE-2011-CIG-303522 to A.C.; ERC-2009-StG-239910 to M.C., and Marie Curie IOF to I.G.-B.), MINECO (CTQ2012–37420-C02-01/BQU and CSD2010-00065 to M.C.), Generalitat de Catalunya (ICREA Academia Award to M.C.), Spanish Ministry of Science (Ramón y Cajal contract to A.C.), and the INNPLANTA project INP-2011-0059-PCT-420000-ACT1 (Dr. X. Ribas). We also thank Dr. Laura Gómez (Serveis Tècnics de Recerca, Universitat de Girona) for helpful advice in setting up the HR-MS experiments, and for fruitful discussions.
Abstract
The bis(μ-oxo)dicopper(III) species [CuIII2(μ-O)2(m-XYLMeAN)]2+ (1) promotes the electrophilic ortho-hydroxylation–defluorination of 2-fluorophenolates to give the corresponding catechols, a reaction that is not accomplishable with a (η2:η2-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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