ortho-C-H Arylation of Benzoic Acids with Aryl Bromides and Chlorides Catalyzed by Ruthenium

A system consisting of catalytic amounts of [(p-cym)RuCl2](2)/PEt3 center dot HBF4, K2CO3 as the base, and NMP as the solvent efficiently mediates the ortho-C-H arylation of benzoic acids with aryl bromides at 100 degrees 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.