title: Mechanistic Analysis of Oxidative C-H Cleavages Using Inter- and Intramolecular Kinetic Isotope Effects.
abstract: A series of monodeuterated benzylic and allylic ethers were subjected to oxidative carbon-hydrogen bond cleavage to determine the impact of structural variation on intramolecular kinetic isotope effects in DDQ-mediated cyclization reactions. These values are compared to the corresponding intermolecular kinetic isotope effects that were accessed through subjecting mixtures of non-deuterated and dideuterated substrates to the reaction conditions. The results indicate that carbon-hydrogen bond cleavage is rate determining and that a radical cation is most likely a key intermediate in the reaction mechanism.
authors.affiliation: Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
authors.forename: Hyung Hoon
authors.initials: HH
authors.lastname: Jung
authors.forename: Paul E
authors.initials: PE
authors.lastname: Floreancig