title: Enantioselective N-heterocyclic carbene-catalyzed β-hydroxylation of enals using nitroarenes: an atom transfer reaction that proceeds via single electron transfer.
abstract: A novel oxidative N-heterocyclic carbene-catalyzed reaction pathway has been discovered. Alkyl and aryl enals undergo β-hydroxylation via oxygen atom transfer from electron-deficient nitrobenzenes, followed by trapping of the resultant acyl azolium by the solvent. The proposed mechanism involves a single electron transfer event to initiate the reaction followed by radical recombination. This represents a profound mechanistic departure from the established two-electron disconnects in NHC catalysis.
authors.affiliation: Department of Chemistry, Colorado State University , Fort Collins, Colorado 80523, United States.
authors.forename: Nicholas A
authors.initials: NA
authors.lastname: White
authors.forename: Tomislav
authors.initials: T
authors.lastname: Rovis
mesh_terms: D001554:Benzene / Q000737:chemistry*; D002384:Catalysis; D004579:Electron Transport; D006571:Heterocyclic Compounds / Q000737:chemistry*; D006900:Hydroxylation; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D013237:Stereoisomerism; D013379:Substrate Specificity
chemical_list: D006571:Heterocyclic Compounds; C030011:carbene; D001554:Benzene; D008697:Methane