Palladium- and Copper-Catalyzed Site Selective Monoamination of Dibromobenzoic Acid

• Published in: Advanced synthesis & catalysis Vol. 353; no. 4; pp. 538 - 544
• Main Authors: Houpis, Ioannis N., Weerts, Koen, Nettekoven, Ulrike, Canters, Martine, Tan, Hongyu, Liu, Renmao, Wang, Youchu
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 07.03.2011; WILEY‐VCH Verlag; Wiley; Wiley-VCH
• Subjects: 2,4‐dibromobenzoic acid; 4-dibromobenzoic acid; Anions; Aromatic compounds; carboxylate directed aminations; Catalysis; Catalysts: preparations and properties; Chemistry; Chemistry, Applied; Chemistry, Organic; copper; Derivatives; Equivalence; Exact sciences and technology; General and physical chemistry; Noncondensed benzenic compounds; Organic chemistry; palladium; Physical Sciences; Preparations and properties; Science & Technology; selective aromatic aminations; Selectivity; Solvents; Synthesis; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; selective aromatic aminations; 2,4-dibromobenzoic acid; DIRECTED ORTHO-METALATION; ARYLATION; C-H BONDS; FUNCTIONALIZATION; CROSS-COUPLING REACTIONS; AMINATION; AMINES; carboxylate directed aminations; copper; palladium; ARYL; EFFICIENT; ULLMANN; Catalytic reaction; Transition metal; Palladium; Selectivity; Benzoic acid derivatives; Anions; Amination; Carboxylate; Benzenic compound; Copper I; Aromatic compound; Catalysis; Platinoid; Solvent
• ISSN: 1615-4150; 1615-4169; 1615-4169
• DOI: 10.1002/adsc.201000800

The carboxylate anion has been used as a directing group in the aromatic amination of electronically equivalent aryl bromides to afford selective ortho‐substituted derivatives (>99:1 selectivity; 60–80% yield) in the case of copper(I) catalysis. The solvent, base and equivalents of base were important factors in the success of this reaction. Complementary selectivity was achieved with palladium catalysis where the para‐substituted derivatives were produced selectively (>99% selectivity, 70–80% yield).