Electrochemical Synthesis of Itaconic Acid Derivatives via Chemodivergent Single and Double Carboxylation of Allenes with CO2

Leveraging electrochemistry, a new synthesis of non‐natural derivatives of itaconic acid is proposed by utilizing carbon dioxide (CO2) as a valuable C1 synthon. An electrochemical cross‐electrophile coupling between allenoates and CO2 was targeted, allowing for the synthesis of both mono‐ and di‐carboxylation products in a catalyst‐ and additive‐free environment (yields up to 87%, 30 examples). Elaboration of the model mono‐carboxylation product, and detailed cyclovoltammetric, as well as mechanistic analyses complete the present investigation.