Greening Organic Electrochemistry: Harnessing Electrogenerated Bases (EGBs) for Sustainable Organic Transformations

Electrogenerated bases (EGBs) are emerging as powerful and sustainable tools in synthetic chemistry, offering cleaner and more efficient alternatives to traditional stoichiometric bases. This Review outlines the fundamental principles of EGB formation and explores their expanding role in enabling diverse and selective organic transformations, including alkylations, trifluoromethylations, Stevens rearrangements, Wittig reactions, esterifications, additions, anionic chain reactions, macrolide formation, polymerizations, C–H deprotonations and functionalizations, condensation reactions, and electrocarboxylation. EGBs efficiently activate substrates bearing labile protons, facilitating the generation of reactive intermediates for key bond-forming steps. These methods enable access to heterocycles, fluorinated compounds, and valuable intermediates relevant to pharmaceutical and materials science. Beyond expanding the synthetic scope, EGBs enhance regio- and stereoselectivity, contributing to greater reaction precision. While batch electrolysis has been widely used, advances in flow electrochemistry offer improved control, safety, and scalability. Innovations such as “ex-cell” reactor designs, where oxidation and reduction steps are spatially separated, further improve efficiency and minimize side reactions. The use of environmentally benign materials-such as electrodes (e.g., magnesium), green solvents, and sustainable electrolytes-significantly influences both performance and sustainability. Despite these advantages, challenges remain including limited substrate tolerance, sensitivity to reaction conditions, and the requirement for specialized electrochemical equipment.