Copper-catalysed electrochemical atom transfer radical addition (eATRA) has emerged as a novel method for C−C bond formation, expanding the scope of electrocatalysis in organic synthesis.1, 2 In this process, a CuI complex activates alkyl halides (RX) through coupled electron and atom transfer, generating organic radicals that are recaptured by CuI complexes to form unusual organocopper(II) intermediates, [CuIILR]+, stabilised by tetradentate N-donor ligands. This [CuIILR]+ intermediate serves as the controlled-release source of radicals, facilitating efficient and selective atom transfer radical addition (ATRA) reactions and minimises unwanted radical homocoupling.1−3
The methodology is applied to various organic halide initiators containing nitrile, keto, ester and amide functional groups, targeting C=C bonds in aromatic alkenes such as styrene and 2-vinyl naphthalene, as well as aliphatic alkenes.4−6 X-ray crystallography, cyclic voltammetry, and UV/Vis spectroelectrochemical studies provided insights into the active organocopper(II) species, offering a detailed understanding of how functional groups influence reactivity. Optimised, mild reaction conditions were employed, presenting a novel approach beyond conventional copper-catalysed C−C bond formation. This presentation will focus on design and synthesis of Cu(II) catalysts, the investigation of their activity under electrochemical conditions, and the potential of Cu(II)-mediated electrochemical methods for developing C–C bonds in organic synthesis.
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