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Palladium-Catalyzed Decarbonylative Trifluoromethylation of Acid Fluorides.

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 R₃ SiCF₃ occurs prior to decarbonylation.

SUBMITTER: Keaveney ST

PROVIDER: S-EPMC5900963 | biostudies-literature | 2018 Apr

REPOSITORIES: biostudies-literature

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Palladium-Catalyzed Decarbonylative Trifluoromethylation of Acid Fluorides.

Keaveney Sinead T ST Schoenebeck Franziska F

Angewandte Chemie (International ed. in English) 20180313 15

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 (ArCF<sub>3</sub> ). The strategy relies on a Pd/Xantphos catalytic system and the supply of fluoride for transmetalation through intramolecular redistribution t ...[more]

PMID: 29479784

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