The Parasram Lab reported the anaerobic cleavage of alkenes using nitroarenes and visible light, which can serve as a practical alternative to classical ozonolysis. The work, entitled “Photoinduced Oxygen Transfer Using Nitroarenes for the Anaerobic Cleavage of Alkenes” was published in the Journal of the American Chemical Society. The contributing authors include co-first authors Dr. Dan Wise and Emma Gogarnoiu, co-second authors Alana Duke, Joshua Paolillo, and Taylor Vacala, along with Dr. Waseem Hussain and Principal Investigator Assistant Professor Marvin Parasram.
Click here to read the full article in JACS.
Abstract: 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 non-stereospecific 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.
The work was supported by generous start-up funds from the Department of Chemistry at New York University