Scalable Electrochemical Decarboxylative Olefination Driven by Alternating Polarity

• Published in: Angewandte Chemie International Edition Vol. 62; no. 42; p. e202309157
• Main Authors: Garrido-Castro, Alberto F., Hioki, Yuta, Kusumoto, Yoshifumi, Hayashi, Kyohei, Griffin, Jeremy, Harper, Kaid C., Kawamata, Yu, Baran, Phil S.
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 16.10.2023; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alkenes; Carboxylic acids; Chemistry; Chemistry, Multidisciplinary; Decarboxylation; Electrochemistry; Physical Sciences; Science & Technology; Synthetic Methods; DECARBONYLATION; Olefination; Decarboxylation; Electrochemistry; Reaction Mechanisms; CARBOXYLIC-ACIDS
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202309157

A mild, scalable (kg) metal-free electrochemical decarboxylation of alkyl carboxylic acids to olefins is disclosed. Numerous applications are presented wherein this transformation can simplify alkene synthesis and provide alternative synthetic access to valuable olefins from simple carboxylic acid feedstocks. This robust method relies on alternating polarity to maintain the quality of the electrode surface and local pH, providing a deeper understanding of the Hofer-Moest process with unprecedented chemoselectivity. The electrochemical conversion of unactivated carboxylic acids to olefins under alternating polarity is reported. By modulating electrode surface quality and local acidity, chemoselective Hofer-Moest reactivity is realized on conventionally difficult substrates, including primary and secondary unactivated carboxylic acids. This simple protocol is exceptionally scalable (1 kg) and cost-effective.**image