Copper-Catalyzed Reactions of Aryl Halides with N-Nucleophiles and Their Possible Application for Degradation of Halogenated Aromatic Contaminants

Abstract

This review summarizes recent applications of copper or copper-based compounds as a nonprecious metal catalyst in N-nucleophiles-based dehalogenation (DH) reactions of halogenated aromatic compounds (Ar-Xs). Cu-catalyzed DH enables the production of corresponding nonhalogenated aromatic products (Ar-Nu), which are much more biodegradable and can be mineralized during aerobic wastewater treatment or which are principally further applicable. Based on available knowledge, the developed Cu-based DH methods enable the utilization of amines for effective cleavage of aryl-halogen bonds in organic solvents or even in an aqueous solution.

The Silent Threat: Exploring the Ecological and Ecotoxicological Impacts of Chlorinated Aniline Derivatives and the Metabolites on the Aquatic Ecosystem

“…The evidence gathered from scientific studies, such as the potential for long-range transport and the persistence of aromatic amines in the environment, highlights the need for stringent regulation and management practices to prevent the release of these chemicals into water bodies [ 73 ]. Efforts should focus on reducing the use with the promotion of alternative substances, for instance, non-halogenated anilines (e.g., methylanilines, nitroanilines, or methoxyanilines) or less toxic aromatic compounds, as intermediates in the industry where chloroanilines are currently used [ 74 ]. On the other hand, it is important to implement effective wastewater treatment processes that have been referred to in the literature for aniline removal, such as Electro-Fenton ® and peroxy-coagulation processes using a flow reactor, implementing the use of a sequencing batch reactor, zero-valent ion coupled with hydrogen peroxide, among others [ 75 , 76 , 77 ].…”

Functionalization of Fe3O4@SiO2 nanoparticles with Cu(i)-thiosemicarbazone complex as a robust and efficient heterogeneous nanocatalyst for N-arylation of N-heterocycles with aryl halides

“…16 Owing to the unique properties and applications of N-aryl Nheterocycles, different synthetic methodologies have been established to afford these important compounds. [17][18][19] These general approaches are involved (i) the nucleophilic aromatic substitution (S N Ar) reactions of electron-decient aryl halides with N-heterocycles, 20 (ii) the treatment of N-heterocycles with aryliodonium salts, 21 (iii) the heterocyclization of appropriate precursors, 22 (iv) the N-arylation of N-heterocycles with aryl boronic acids, 8,23 (v) Ullmann-type C-N cross coupling reaction between aryl halides and heterocycles. 24,25 However, these protocols are oen associated with numerous shortcomings such as the use of the stoichiometric amount of Cu catalyst, the relative instability and high cost of boronic acids, the use of toxic and expensive ligands, harsh reaction conditions, unavailability of some precursors, and limited scope.…”

“…In this context, numerous Cucatalyzed Ullmann-type C-N cross coupling reactions have been described over the years. 18,31 Nevertheless, several problems were associated with these methods such as less activity because of the low surface area of the catalyst, long reaction time, the use of toxic and sensitive ligands, by-product formation, and the low yields causing a remarkable need for further development of more efficient catalytic systems to achieve the desired N-aryl N-heterocycles.…”

Recent Achievements in the Copper-Catalyzed Arylation of Adamantane-Containing Amines, Di- and Polyamines

“…Further, a more thorough review has been published [46], and some accounts emphasize the application of the method to the synthesis of natural compounds [47,48]. During the last decade, the achievements in the copper-catalyzed amination became a focus of three comprehensive studies [49][50][51], and special cases of this approach have also been discussed recently [52,53].…”