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Chemoselective Aliphatic C–H Bond Oxidation Enabled by Polarity Reversal
Dantignana, Valeria; Milan, Michela; Cussó Forest, Olaf; Company Casadevall, Anna; Bietti, Massimo; Costas Salgueiro, Miquel
Ministerio de Economía y Competitividad (Espanya)
Methods for selective oxidation of aliphatic C–H bonds are called on to revolutionize organic synthesis by providing novel and more efficient paths. Realization of this goal requires the discovery of mechanisms that can alter in a predictable manner the innate reactivity of these bonds. Ideally, these mechanisms need to make oxidation of aliphatic C–H bonds, which are recognized as relatively inert, compatible with the presence of electron rich functional groups that are highly susceptible to oxidation. Furthermore, predictable modification of the relative reactivity of different C–H bonds within a molecule would enable rapid diversification of the resulting oxidation products. Herein we show that by engaging in hydrogen bonding, fluorinated alcohols exert a polarity reversal on electron rich functional groups, directing iron and manganese catalyzed oxidation toward a priori stronger and unactivated C–H bonds. As a result, selective hydroxylation of methylenic sites in hydrocarbons and remote aliphatic C–H oxidation of otherwise sensitive alcohol, ether, amide, and amine substrates is achieved employing aqueous hydrogen peroxide as oxidant. Oxidations occur in a predictable manner, with outstanding levels of product chemoselectivity, preserving the first-formed hydroxylation product, thus representing an extremely valuable tool for synthetic planning and development
Financial support for this work was provided by the Spanish Ministry of Science (CTQ2015-70795-P to M.C., CTQ2016-77989-P to A.C.) and Generalitat de Catalunya (ICREA Academia Award to M.C. and 2014 SGR 862). The authors thank the European Commission for the NoNoMeCat project (675020-MSCA-ITN-2015-ETN)
Oxidació
Oxidation
Compostos orgànics -- Síntesi
Organic compounds -- Synthesis
Tots els drets reservats
Article
info:eu-repo/semantics/publishedVersion
peer-reviewed
American Chemical Society
         

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