Abstract

A catalytic methodology leveraging Electron Donor-Acceptor (EDA) complexes was developed to generate radicals, which were subsequently utilized to synthesize valuable products. An alternative to photocatalysts was provided by this approach, addressing significant drawbacks such as the high cost and environmental concerns associated with precious metal-based photocatalysts like ruthenium and iridium, which present scalability challenges. Although organic dyes have been used as substitutes, their major limitation lies in their stability. Three distinct projects were encompassed in this research, each demonstrating the efficacy of this novel strategy. The first project focuses on the metal-free trifluoromethylthiolation of terminal alkenes. Here, an EDA complex is formed between trifluoromethylthio phthalimide and tetrabutylammonium iodide. A catalytic amount of the donor is employed, as it is regenerated within the catalytic cycle, ensuring efficiency and sustainability. The second project explores a C(sp3)–C(sp2) nickel-catalyzed cross-coupling reaction. In this approach, an EDA complex is formed between an electron donor and an alkyl iodide to generate an alkyl radical, which is subsequently captured by a nickel catalyst, facilitating the desired cross-coupling reaction. 3 The final project investigates a nickel-catalyzed cross-coupling reaction between acyl electrophiles and radical precursors. The goal is to develop a cross coupling methodology utilizing widely available starting materials, such as car boxylic acids and alcohol derivatives. An EDA complex is formed between H¨ unig’s base and N-alkoxyphthalimide, enabling the efficient formation of the desired products. Overall, a cost-effective, environmentally friendly alternative to traditional photocatalysts is offered by this research, advancing the field of radical generation and catalytic cross-coupling reactions.