title: Oxidation of some cage hydrocarbons by dioxiranes. Nature of the transition structure for the reaction of C-H bonds with dimethyldioxirane: a comparison of B3PW91 density functional theory with experiment.
abstract: Dimethyl- (DMD) and methyl(trifluoromethyl)-dioxiranes were used for oxyfunctionalization of spiro{1',7-cyclopropan-(E)-2-methylbicyclo[2.2.1]heptane} (), tricyclo[3.2.2.0(2,4)]nonane (), exo-endo-endo- () and exo-exo-exo- () heptacyclo[9.3.1.0(2,10).0(3,8).0(4,6).0(5,9).0(12,14)]pentadecane, yielding tertiary alcohols as the main products. The rate constants for oxidation of by DMD were measured and the Arrhenius parameters determined. The DFT theory (B3LYP and B3PW91) using restricted and unrestricted methods was employed to study the oxidation reaction of the C-H bond of cage hydrocarbons , adamantane, and acetone with DMD. The kinetic isotopic effect calculated using unrestricted methods agreed with experiment. The reaction mechanism in terms of the concerted oxygen insertion vs. the radical part is discussed.
authors.affiliation: Institute of Organic Chemistry, Ufa Research Centre of the Russian Academy of Sciences, 71 prosp. Oktyabrya, 450054 Ufa, Russia. stas_g@anrb.ru, stas_g@isof.cnr.it
authors.forename: Stanislav A
authors.initials: SA
authors.lastname: Grabovskiy
authors.forename: Arcadiy V
authors.initials: AV
authors.lastname: Antipin
authors.forename: Elena V
authors.initials: EV
authors.lastname: Ivanova
authors.forename: Vladimir A
authors.initials: VA
authors.lastname: Dokichev
authors.forename: Yuriy V
authors.initials: YV
authors.lastname: Tomilov
authors.forename: Natalie N
authors.initials: NN
authors.lastname: Kabal'nova