Organocuprate Cross‐Coupling: The Central Role of the Copper(III) Intermediate and the Importance of the Copper(I) Precursor

Copper(I) Phenoxide Complexes in the Etherification of Aryl Halides

“…Experiments that probe for redox processes and the generation of free or caged aryl radicals provide strong evidence against these process to form such radical intermediates and argue in favor of an oxidative addition to form an arylCu III phenoxide complex that undergoes reductive elimination of ether. Although Cu III species are not common, alkylcopper(III) [31][32][33][34] and arylcopper(III) [11,35] species have been identified recently. Moreover, we have conducted computational studies by DFT on the energy of a phen-ligated arylcopper(III) halide phenoxide complex, and the ΔG for formation of this species from the [Cu(phen)(OPh)] and PhI is computed to be 22.1 kcalmol −1 [Eq.…”

Understanding the stability, electronic and molecular structure of some copper(III) complexes containing alkyl and non alkyl ligands: Insights from DFT calculations

“…Gschwind et al have stabilized the first Cu(III) intermediate of a substitution reaction of Gilman cuprates with alkyl halides in diethyl ether [10]. Simultaneously, Bertz and Ogle et al have investigated the reactions of a variety of methyl Gilman reagents (Me 2 CuLi$LiX (X ¼ I, CN, SCN, SPh)) with a simple alkyl halide (EtI) under RI-NMR conditions and found different stabilities for several TCSP Cu(III) intermediates [11,12]. In 2008, Bertz and Ogle et al have investigated the structure of some neutral organocopper(III) complexes from organocopper(I) reagents and alkyl halides (EtI) in the presence of certain strong electron donating ligands [13].…”

Neutral organocopper(iii) complexes

“…1,2 The trans-coupling ( 2 J = 130.4 Hz) between P and the methylene C atom in CH 3 13 CH 2 ( 13 CH 3 ) 2 Cu(PBu 3 ) is much larger than the cis-coupling ( 2 J = 14.6 Hz) of P with the methyl C atoms (see Fig. 1), which is also the general case for Pt complexes.…”