Research Projects

In the field of modern organic chemistry and pharmaceuticals, it is in high demand to develop more sustainable, enantioselective synthetic methodologies for the synthesis of enantiopure biologically active chiral molecules. In that manner, electrochemical methods provide a more efficient, environmentally friendly alternative to conventional synthesis. In this project proposal, a novel methodology for enantioselective electrochemical synthesis is proposed by accessing alternating current electrolysis with chiral ligated nickel catalysts. This methodology aims to expand the asymmetric catalysis by enabling electrochemical energy to achieve enantioselective C-C bond formations. So far, most electrochemical syntheses have been established with direct current (DC) electrolysis or paired electrolysis, which includes constant current and constant potential. In DC electrolysis or paired electrolysis, either oxidation or reduction reaction depends on working electrodes transferring electrons to the substrate or mediator. However, this paired electrolysis shows that slow mass transfer between two electrodes and short-lived intermediates may lead to poor reactivity and reaction selectivity. Long-lived stable intermediates are required for efficient reaction. This work deals with these limitations by merging chiral ligand-enabled nickel catalysis with alternating current electrolysis, enabling precise control over oxidation and reduction steps in a time-resolved manner. This method is expected to provide a new approach for radical-polar crossover and enantioselective radical capture in multistep nickel-catalyzed reactions. The project will involve designing suitable chiral nickel complexes and optimizing various parameters such as frequency, current, and potential to enhance selectivity. Mechanistic understanding of radical and ionic intermediates will be carried out in a detailed manner. This methodology will explore enantioselective synthesis of biologically active molecules through C-C bond formation using chiral nickel catalysts under AC electrolysis. To construct C-C bond, various strategies were used in this proposal, such as enantioselective reductive cross-coupling α-arylation via enolonium ions, asymmetric acylation via acyl radicals, asymmetric hydroalkynylation or hydroalkenylation via alkene radicals, enantioselective reductive cross-coupling of aryl aziridines with alkenyl bromides via benzyl radicals, and Enantioselective synthesis of spiro compounds via radical cascade cyclization. This sustainable and innovative approach will open up new avenues in asymmetric synthesis, which will offer high enantioselectivity, broad functional group tolerance, and minimal waste.

Alternating current, electrodes, radicals, asymmetric, nickel catalysts, chiral ligands.