Cu(i)/Amino Acid Catalyzed Coupling Reactions of Aryl Halides and Nucleophiles: Applications in Large-scale Production

Abstract

Amino acids can be used as ligands to promote Ullmann-type coupling reactions. This review briefly discusses how L-proline, 4-hydroxy-L-proline and N,N-dimethylglycine can serve as the ideal ligands for copper-catalyzed coupling of aryl halides with different nucleophiles. Seven examples of applications of copper/amino acid catalyzed reactions in large-scale preparations are described.

The Influence of Copper on Halogenation/Dehalogenation Reactions of Aromatic Compounds and Its Role in the Destruction of Polyhalogenated Aromatic Contaminants

“…The arylation in 100 kg scale of 4-bromo-chlorobenzene using 4-methoxyphenol was reported under the above-described conditions using L7 (Figure 2) as the cheap ligand of choice producing exclusively 4-chlorophenyl-4 -methoxyphenylether. In this case, the coupling reaction worked well at 90 • C in dioxane using Cs 2 CO 3 as a base, and a wide range of aryl iodides, aryl bromides and phenols could be used as coupling partners [107].…”

“…Scheme 23. Cu-catalyzed formation of 2,5-dihydroxyterephtalic acid from 2,5-dihalogenoterephtalic acid [82,107].…”

Recent Synthetic Developments and Applications of the Ullmann Reaction. A Review

“…33 Ma and coworkers reviewed the developments and applications of amino acid-based ligands in copper-catalyzed coupling reactions. 27, 34 Comparison of palladium- and copper-catalyzed coupling reactions was described by Senra 35 and Koenig. 36 The development of copper-catalyzed formations of C-N, C-O, and C-C bonds, since 2004, was highlighted by Monnier and Taillefer.…”