In this joint project the mechanism and scope of a new electrooxidative biaryl coupling of substituted arenes will be explored and defined. This electrochemical approach has the advantage that no leaving functionalities are required for biaryl cross-coupling. Since no reagent waste is formed in this reagent- and metal free electroorganic process, a highly sustainable synthetic method will be established. The use of electricity and solvent effects to direct the selectivity of the cross-coupling creates a cutting-edge technique in contemporary organic synthesis. This concept based on the decoupling of nucleophilicity and oxidation potential of the substrates can be considered as a new type of umpolung and allows outstanding coupling selectivity. The efficiency of this new methodology will be exploited for the efficient and modular synthesis of mimetics for α-helices based on teraryl and quateraryl architectures. The strategy involves a complementary combination of modern metal-catalyzed steps as well as electrosynthetic transformations which do not require leaving functionalities and provide a direct and sustainable access to such entities.