title: Radical cation ester cleavage in solution: mechanism of the mesolytic O-CO bond scission.
abstract: A wide range of enol carbonate, carbamate, and ester radical cations is characterized in solution by cyclic voltammetry and EPR spectroscopy. Preparative transformations using one-electron oxidants or anodic oxidation yield benzofurans after O-CO bond cleavage. Mechanistic investigations and direct detection of radical intermediates reveal that all enol radical cations undergo exclusively O-CO bond cleavage to provide alpha-carbonyl cations and acyl (or alternatively, alkoxyacyl and aminoacyl) radicals, respectively. The kinetics of the mesolytic fragmentation and the influence of nucleophilic additives have been determined using fast-scan cyclic voltammetry.
authors.affiliation: FB 8 - OC1 (Chemie-Biologie) der Universität-GH Siegen, Adolf-Reichwein-Strasse, D-57068 Siegen, Germany. schmittel@chemie.uni-siegen.de
authors.forename: M
authors.initials: M
authors.lastname: Schmittel
authors.forename: K
authors.initials: K
authors.lastname: Peters
authors.forename: E M
authors.initials: EM
authors.lastname: Peters
authors.forename: A
authors.initials: A
authors.lastname: Haeuseler
authors.forename: H
authors.initials: H
authors.lastname: Trenkle