Economical, Green, and Safe Route Towards Substituted Lactones by Anodic Generation of Oxycarbonyl Radicals

• Published in: Angewandte Chemie Vol. 131; no. 45; pp. 16261 - 16264
• Main Authors: Petti, Alessia, Leech, Matthew C., Garcia, Anthony D., Goodall, Iain C. A., Dobbs, Adrian P., Lam, Kevin
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 04-11-2019
• Subjects: Chemistry; Electrochemistry; Elektrochemie; Elektrosynthese; Grüne Chemie; Lactone; Lactones; Organic chemistry; Radicals; Radikalische Cyclisierung; Salts
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201909922

A new electrochemical methodology has been developed for the generation of oxycarbonyl radicals under mild and green conditions from readily available hemioxalate salts. Mono‐ and multi‐functionalised γ‐butyrolactones were synthesised through exo‐cyclisation of these oxycarbonyl radicals with an alkene, followed by the sp3–sp3 capture of the newly formed carbon‐centred radical. The synthesis of functionalised valerolactone derivatives was also achieved, demonstrating the versatility of the newly developed methodology. This represents a viable synthetic route towards pharmaceutically important fragments and further demonstrates the practicality of electrosynthesis as a green and economical method to activate small organic molecules.
Sauberer Strom: Eine neue elektrochemische Methode erzeugt Oxycarbonylradikale unter milden Bedingungen aus leicht verfügbaren Hemioxalatsalzen. Mono‐ und multifunktionalisierte γ‐Butyrolactone wurden durch exo‐Cyclisierung dieser Oxycarbonylradikale mit einem Alken synthetisiert, gefolgt vom sp3‐sp3‐Abfang des neu gebildeten kohlenstoffzentrierten Radikals.