Copper-Catalyzed Coupling of Aryl Halides with Amines, Alcohols, and Thiols

Mechanism of Copper-Catalyzed Coupling of Aryl Halides with Amines, Alcohols, and Thiols 

Network of various proposed mechanisms for the reaction of copper alkoxides, amides, and amides with aryl halides. 

More detailed mechanistic studies have been conducted with isolated ligated copper complexes, along with kinetic studies on reactions catalyzed by complexes of diamine ligands. These studies have shown that copper(I) amidate and imidate complexes are competent to be intermediates in the catalytic coupling of aryl halide with amides and imi-des. These studies also implied that two-coordinate anionic cuprate complexes undergo oxidative addition of the aryl halide more slowly than do related three-coordinate, neutral copper complexes containing a bidentate dative ligand. This conclusion is shown clearly by the formation of coupled product from iodotoluene and the species that equilibrates between the ionic and three-coordinate neutral species (Equation 19.119) and the lack of 

CHAPTER 19 TRANSITION METAL-CATALYZED COUPLING REACTIONS 

Reactions of Aryl Boronic Acids with Amines and Aicohols (Chan-Evans-Lam Couplings) 

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