Carbon–carbon (C–C) bond formation is fundamental to building molecular frameworks in pharmaceuticals, agrochemicals, and materials, making efficient C–C bond-forming methods a central goal in organic synthesis. Electrochemistry has emerged as a sustainable and versatile tool, enabling challenging transformations under mild conditions. Although organocopper(I) complexes are widely applied in C–C and C–heteroatom bond formation, organocopper(II) species remain underexplored.
This work develops and optimises electrochemical atom transfer radical addition (eATRA) as a sustainable approach to C–C bond construction using diverse alkenes and organocopper catalysts, supported by mechanistic investigations. Expanding the reaction scope with mono- and polyhalogenated initiators revealed an unexpected two-step eATRA–cyclisation pathway with functionalised styrenes and diethyl halomalonates, affording the corresponding cyclopropanes. As cyclopropanes are highly valued motifs in medicinal chemistry, this work reveals new reactivity in electrochemical copper catalysis and expands its synthetic utility.