Effect of Alternating Polarity in Electrochemical Olefin Hydrocarboxylation

Abstract The electrochemical generation of radical anions from feedstock olefins offers a selective and efficient route for synthesizing commodity chemicals and pharmaceutical precursors via hydrofunctionalization. Traditional methods for electrochemical olefin hydrofunctionalization, for example, hydrocarboxylation, rely on anion intermediates and follow an electrochemical–chemical–electrochemical–chemical (ECEC) mechanism involving olefin reduction, carboxylation, further reduction, and protonation. Enhancing terminal carboxylate selectivity often requires a proton source, reducing functional group tolerance and favoring proton reduction over olefin reduction. Alternating polarity, a nascent technique in organic electrochemistry, can improve product selectivity by influencing electron transfer rates and electrode surface species. Herein, we report the use of alternating polarity to selectively generate radical anions from styrene derivatives, using electrochemical hydrocarboxylation as a model. This approach shifts the mechanism to an electrochemical–chemical–chemical (ECC) pathway, where the final step involves hydrogen atom transfer. We showcase how alternating polarity modulates product selectivity, yield, and material decomposition, offering new insights into how alternating polarity can advance olefin functionalization by enabling more controlled and selective reaction pathways.