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

Chemistry. 2024 Sep 2;30(49):e202401754. doi: 10.1002/chem.202401754. Epub 2024 Aug 13.

Abstract

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.

Keywords: Allenoates; CO2; Carboxylation; Electrosynthesis; Itaconic acid.

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