Cathode Material Determines Product Selectivity for Electrochemical C−H Functionalization of Biaryl Ketoximes

• Published in: Angewandte Chemie International Edition Vol. 57; no. 46; pp. 15153 - 15156
• Main Authors: Zhao, Huai‐Bo, Xu, Pin, Song, Jinshuai, Xu, Hai‐Chao
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 12.11.2018; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Cathodes; Chemistry; Chemistry, Multidisciplinary; C−H functionalization; Dehydrogenation; Deoxygenation; Electrochemistry; Electrode materials; heterocycles; Heterocyclic compounds; Oxides; oximes; paired electrolysis; Physical Sciences; radicals; Science & Technology; Selectivity; Substrates; radicals; paired electrolysis; C-H functionalization; N-OXIDES; oximes; GREEN; RADICAL FORMATION; STRATEGIES; METHODOLOGY; heterocycles; NITRILES; GENERATION; ORGANIC ELECTROSYNTHESIS; C−H functionalization
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201809679

The synthesis of polycyclic N‐heteroaromatic compounds and their corresponding N‐oxides has been developed through electrochemical C−H functionalization of biaryl ketoximes. The oxime substrates undergo dehydrogenative cyclization when a Pt cathode is used, resulting in unprecedented access to a wide range of N‐heteroaromatic N‐oxides. The products of the electrosynthesis are switched to the deoxygenated N‐heteroaromatics by employing a Pb cathode through sequential anode‐promoted dehydrogenative cyclization and cathodic cleavage of the N−O bond in the initially formed N‐oxide. Split personality: A divergent synthesis of polycyclic N‐heteroaromatics and the corresponding N‐oxides through electrochemical C−H functionalization of biaryl ketoximes has been developed. The choice of the cathode material controls product selectivity.