Oxygenation of Alkane C−H Bonds with Methyl(trifluoromethyl)dioxirane: Effect of the Substituents and the Solvent on the Reaction Rate

The mechanism of the oxygenation of alkane C−H bonds with methyl(trifluoromethyl)dioxirane
(1a) is studied through the effect of the substituent and solvent on the rate of oxygenation of
2-substituted adamantanes (2). The results suggest a remarkable electron deficiency at the reacting
carbon atom in the transition state leading to the regular oxygenation products. The linearity of
the Hammett plot reveals that the reaction mechanism does not change within a range of
0.15−0.67 units of σI. A change in the solvent does not affect the distribution of the products,
indicating a through-bond transmission of the substituent effect as the origin of the deactivation
of the substrate.