Nitrosobenzene-mediated C-C bond cleavage reactions and spectral observation of an oxazetidin-4-one ring system.
While bond formation processes have traditionally garnered the attention of the chemical community, methods facilitating bond breaking remain relatively undeveloped. We report a novel, transition-metal-free oxidative C-C bond cleavage process for a broad range of ester and dicarbonyl compounds involving carbanion addition to nitrosobenzene. ReactIR experiments on the nitrosobenzene-mediated oxidative decarboxylation of esters indicate the reaction proceeds via fragmentation of a previously unobserved oxazetidin-4-one heterocycle, characterized by an intense IR stretching frequency at 1846 cm-1. These mechanistic studies have allowed further expansion of this protocol to ketone cleavage reactions of a diverse array of beta-ketoester and 1,3-diketone substrates. The conceptual and mechanistic insights offered by this study are likely to provide a platform for further development of bond-breaking methodologies.
Payette
Joshua N
JN
Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue, Chicago, Illinois 60637, USA.
Yamamoto
Hisashi
H
D001384:Azetidines / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry; D004952:Esters / Q000737:chemistry; D009603:Nitroso Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D013055:Spectrophotometry, Infrared / Q000379:methods*
D001384:Azetidines; D002264:Carboxylic Acids; D004952:Esters; D009603:Nitroso Compounds; C012456:nitrosobenzene