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Palladium‐Catalyzed Decarbonylative Trifluoromethylation of Acid Fluorides
Author(s) -
Keaveney Sinead T.,
Schoenebeck Franziska
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201800644
Subject(s) - transmetalation , xantphos , decarbonylation , trifluoromethylation , chemistry , catalysis , palladium , trifluoromethyl , stille reaction , organic chemistry , fluoride , combinatorial chemistry , inorganic chemistry , alkyl
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 3 ). 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 R 3 SiCF 3 occurs prior to decarbonylation.