Overriding Intrinsic Reactivity in Aliphatic C−H Oxidation: Preferential C3/C4 Oxidation of Aliphatic Ammonium Substrates

The site‐selective C−H oxidation of unactivated positions in aliphatic ammonium chains poses a tremendous synthetic challenge, for which a solution has not yet been found. Here, we report the preferential oxidation of the strongly deactivated C3/C4 positions of aliphatic ammonium substrates by emplo...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2020-07, Vol.59 (30), p.12387-12391
Main Authors: Knezevic, Melina, Heilmann, Michael, Piccini, Giovanni Maria, Tiefenbacher, Konrad
Format: Article
Language:English
Subjects:
Aliphatic compounds
Ammonium
Catalysis
Catalysts
Chemical reactions
Chemical synthesis
C−H oxidation
Deactivation
molecular recognition
Oxidation
regioselectivity
Substrates
supramolecular chemistry
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Summary:The site‐selective C−H oxidation of unactivated positions in aliphatic ammonium chains poses a tremendous synthetic challenge, for which a solution has not yet been found. Here, we report the preferential oxidation of the strongly deactivated C3/C4 positions of aliphatic ammonium substrates by employing a novel supramolecular catalyst. This chimeric catalyst was synthesized by linking the well‐explored catalytic moiety Fe(pdp) to an alkyl ammonium binding molecular tweezer. The results highlight the vast potential of overriding the intrinsic reactivity in chemical reactions by guiding catalysis using supramolecular host structures that enable a precise orientation of the substrates. A supramolecular tweezer catalyst has been synthesized that is capable of oxidizing aliphatic ammonium salts at the deactivated methylene positions C3/C4. The catalyst is able to override the intrinsic reactivity in the C−H oxidation of these substrates.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202004242