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Palladium-Catalyzed Decarbonylative Trifluoromethylation of Acid Fluorides

Journal Article


Abstract


  • While acid fluorides can readily be made from widely available or biomass-feedstock-derived carboxylic acids, their use as functional groups in metal-catalyzed cross-coupling reactions is rare. This report presents the first demonstration of Pd-catalyzed decarbonylative functionalization of acid fluorides to yield trifluoromethyl arenes (ArCF3). The strategy relies on a Pd/Xantphos catalytic system and the supply of fluoride for transmetalation through intramolecular redistribution to the the Pd center. This strategy eliminated the need for exogenous and detrimental fluoride additives and allows Xantphos to be used in catalytic trifluoromethylations for the first time. Our experimental and computational mechanistic data support a sequence in which transmetalation by R3SiCF3 occurs prior to decarbonylation.

Publication Date


  • 2018

Citation


  • Keaveney, S. T., & Schoenebeck, F. (2018). Palladium-Catalyzed Decarbonylative Trifluoromethylation of Acid Fluorides. Angewandte Chemie - International Edition, 57(15), 4073-4077. doi:10.1002/anie.201800644

Scopus Eid


  • 2-s2.0-85043508557

Start Page


  • 4073

End Page


  • 4077

Volume


  • 57

Issue


  • 15

Abstract


  • While acid fluorides can readily be made from widely available or biomass-feedstock-derived carboxylic acids, their use as functional groups in metal-catalyzed cross-coupling reactions is rare. This report presents the first demonstration of Pd-catalyzed decarbonylative functionalization of acid fluorides to yield trifluoromethyl arenes (ArCF3). The strategy relies on a Pd/Xantphos catalytic system and the supply of fluoride for transmetalation through intramolecular redistribution to the the Pd center. This strategy eliminated the need for exogenous and detrimental fluoride additives and allows Xantphos to be used in catalytic trifluoromethylations for the first time. Our experimental and computational mechanistic data support a sequence in which transmetalation by R3SiCF3 occurs prior to decarbonylation.

Publication Date


  • 2018

Citation


  • Keaveney, S. T., & Schoenebeck, F. (2018). Palladium-Catalyzed Decarbonylative Trifluoromethylation of Acid Fluorides. Angewandte Chemie - International Edition, 57(15), 4073-4077. doi:10.1002/anie.201800644

Scopus Eid


  • 2-s2.0-85043508557

Start Page


  • 4073

End Page


  • 4077

Volume


  • 57

Issue


  • 15