Photoinduced Oxygen Transfer Using Nitroarenes for the Anaerobic Cleavage of Alkenes

• Published in: Journal of the American Chemical Society Vol. 144; no. 34; pp. 15437 - 15442
• Main Authors: Wise, Dan E., Gogarnoiu, Emma S., Duke, Alana D., Paolillo, Joshua M., Vacala, Taylor L., Hussain, Waseem A., Parasram, Marvin
• Format: Journal Article
• Language: English
• Published: American Chemical Society 31-08-2022
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.2c05648

Herein we report the anaerobic cleavage of alkenes into carbonyl compounds using nitroarenes as oxygen transfer reagents under visible light. This approach serves as a safe and practical alternative to mainstream oxidative cleavage protocols, such as ozonolysis and the Lemieux–Johnson reaction. A wide range of alkenes possessing oxidatively sensitive functionalities underwent anaerobic cleavage to generate carbonyl derivatives with high efficiency and regioselectivity. Mechanistic studies support that the transformation occurs via direct photoexcitation of the nitroarene followed by a nonstereospecific radical cycloaddition event with alkenes. This leads to 1,3,2- and 1,4,2-dioxazolidine intermediates that fragment to give the carbonyl products. A combination of radical clock experiments and in situ photoNMR spectroscopy revealed the identities of the key radical species and the putative aryl dioxazolidine intermediates, respectively.