Selective Electrosynthetic Hydrocarboxylation of α,β‐Unsaturated Esters with Carbon Dioxide**

The carboxylation of low-value commodity chemicals to provide higher-value carboxylic acids is of significant interest. Recently alternative routes to the traditional hydroformylation processes that used potentially toxic carbon monoxide and a transition metal catalyst have appeared. A significant challenge has been the selectivity observed for olefin carboxylation. Photochemical methods have shown a viable route towards the hydrocarboxylation of α,β-unsaturated alkenes but rely on the use of an excess reducing or amine reagent. Herein we report our investigations of an electrochemical approach that is able to hydrocarboxylate α,β-unsaturated alkenes with excellent regioselectivity and the ability to carboxylate hindered substrates to afford α-quaternary center carboxylic acids. The reported process requires no chromatography and the products are purified by simple crystallization from the reaction mixture after work-up.