Electrosinthesys in modern organic chemistry: from CO2 fixation to the diversification of bio-relevant scaffolds

Electroorganic synthesis offers a sustainable alternative to traditional redox methodologies by replacing stoichiometric oxidants and reductants with electrons as traceless redox mediators, thereby improving atom economy and reducing waste. Despite its historical roots, its broader adoption has been limited by practical considerations. This thesis demonstrates the strategic value of electrosynthesis by developing of innovative methodologies for the construction and selective functionalization of synthetically relevant molecular scaffolds. An initial study describes a catalyst- and additive-free electrochemical crosselectrophile coupling between allenoates and carbon dioxide (CO2), enabling the chemodivergent synthesis of mono- and dicarboxylated non-natural itaconic acid derivatives (up to 87% yield, 30 examples). Mechanistic insights were obtained through cyclic voltammetry. Expanding electroreductive radical approaches, the first site-selective electrochemical alkylation of tropones was achieved via coupling of 2-acetoxytropones with redoxactive esters, affording mono- and disubstituted products under mild conditions with broad functional group tolerance (27 examples). Voltammetric studies clarified the mechanistic profile. Complementarily, a nickel-mediated electroreductive C(sp²)–H functionalization of tropones with aldehydes enabled selective α-alkylation across a wide substrate scope (44 examples, up to 90% yield). Combined electrochemical, spectroelectrochemical, and computational analyses elucidated the catalytic pathway and the key role of reduced nickel species. Finally, a general electrosynthetic strategy for the preparation and direct functionalization of 2-oxabicyclo[2.1.1]hexanes from bicyclo[1.1.0]butane precursors was developed. The anodic generation of electrophilic heteroatom-centered species enabled selective C(4) functionalization under mild, oxidant-free conditions. Mechanistic studies support a pathway involving anodic trigger formation followed by intramolecular cyclization, while late-stage functionalization and bioconjugation highlight the relevance of these scaffolds as benzene bioisosteres in drug discovery.