Catalyst‐Free Decarboxylation of Carboxylic Acids and Deoxygenation of Alcohols by Electro‐Induced Radical Formation

Abstract Electro‐induced reduction of redox active esters and N ‐phthalimidoyl oxalates derived from naturally abundant carboxylic acids and alcohols provides a sustainable and inexpensive approach to radical formation via undivided electrochemical cells. The resulting radicals are trapped by an electron‐poor olefin or hydrogen atom source to furnish the Giese reaction or reductive decarboxylation products, respectively. A broad range of carboxylic acid (1°, 2°, and 3°) and alcohol (2° and 3°) derivatives are applicable in this catalyst‐free reaction, which tolerated a diverse range of functional groups. This method features simple operation, is a sustainable platform, and has broad application.