Stanislav Grabovskiy - 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

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  Publication Details (including relevant citation   information):

  Org. Biomol. Chem.,   2007,5, pp. 2302-2310.

  DOI:  10.1039/B707753J


  Dimethyl- (DMD) and   methyl(trifluoromethyl)-dioxiranes were used for   oxyfunctionalization of   spiro{1′,7-cyclopropan-(E)-2-methylbicyclo[2.2.1] heptane} (1),   tricyclo[,4)]nonane (2), exo-endo-endo- (3) and   exo-exo-exo- (4) heptacyclo[,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 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   agreed with experiment. The reaction mechanism in terms of the   concerted oxygen insertion vs. the radical part is   discussed.

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