Ortho‐C−H Arylation of Benzoic Acids with Aryl Bromides and Chlorides Catalyzed by Ruthenium. Issue 47 (21st October 2016)

• Record Type: Journal Article
• Authors: Biafora, Agostino; Krause, Thilo; Hackenberger, Dagmar; Belitz, Florian; Gooßen, Lukas J.
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 47(2016)
• Page Start: 14752
• Page End: 14755
• Publication Date: 2016-10-21
• Subjects: aryl halides -- benzoic acids -- biaryls -- C−H arylation -- ruthenium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201607270
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A system consisting of catalytic amounts of [( p ‐cym)RuCl2 ]2 /PEt3 ⋅HBF4, K2 CO3 as the base, and NMP as the solvent efficiently mediates the ortho ‐C−H arylation of benzoic acids with aryl bromides at 100 °C. Replacing the phosphine ligand with the amino acid dl ‐pipecolinic acid enables the analogous transformation with aryl chlorides. The key advantage of this broadly applicable transformation is the use of an inexpensive ruthenium catalyst in combination with simple carboxylates as directing groups, which can either be tracelessly removed or used as anchor points for decarboxylative ipso substitutions. Abstract : Bromides and chlorides : A system consisting of [( p ‐cym)RuCl2 ]2 /PEt3 ⋅HBF4 as the catalyst, K2 CO3 as the base, and NMP as the solvent efficiently mediates the ortho ‐C−H arylation of benzoic acids with aryl bromides at 100 °C. Replacing the phosphine ligand with the amino acid dl ‐pipecolinic acid enables the analogous transformation with aryl chlorides.