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ortho ‐C−H Arylation of Benzoic Acids with Aryl Bromides and Chlorides Catalyzed by Ruthenium
Author(s) -
Biafora Agostino,
Krause Thilo,
Hackenberger Dagmar,
Belitz Florian,
Gooßen Lukas J.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201607270
Subject(s) - ruthenium , chemistry , aryl , phosphine , catalysis , benzoic acid , combinatorial chemistry , ligand (biochemistry) , solvent , base (topology) , medicinal chemistry , organic chemistry , alkyl , mathematical analysis , biochemistry , receptor , mathematics
A system consisting of catalytic amounts of [( p ‐cym)RuCl 2 ] 2 /PEt 3 ⋅HBF 4 , K 2 CO 3 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.