Dimethyl- (DMD) and methyl(trifluoromethyl)-dioxiranes were used for oxyfunctionalization of spiro{1',7-cyclopropan-2-(E)-methyl-bicyclo[2.2.1]heptane} (1), tricyclo[3.2.2.0(2,4)]nonane (2), exo-endo-endo- (3) and exo-exo-exo-heptacyclo¬[9.3.1.0(2,10).0(3,8).0(4,6).0(5,9).0(12,14)]pentadecane (4), yielding tertiary alcohols as the main products. The rate constants for oxidation of 1-4 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 1-4, adamantane, and acetone with DMD. The kinetic isotopic effect calculated using unrestricted methods agree with experiment. The reaction mechanism in terms of the concerted oxygen insertion vs the radical part is discussed.
2007, V.5, No.14, 2302 – 2310