title: Oxygenation of alkane C-H bonds with methyl(trifluoromethyl)dioxirane: effect of the substituents and the solvent on the reaction rate.
abstract: [Chemical reaction: See text] 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 sigma(I). 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.
authors.affiliation: Departamento de Química Orgánica, Universidad de Valencia, Avda. V. Andrés Estellés s/n, 46100-Burjassot, Valencia, Spain.
authors.forename: María E
authors.initials: ME
authors.lastname: González-Núñez
authors.forename: Jorge
authors.initials: J
authors.lastname: Royo
authors.forename: Rossella
authors.initials: R
authors.lastname: Mello
authors.forename: Minerva
authors.initials: M
authors.lastname: Báguena
authors.forename: Jaime Martínez
authors.initials: JM
authors.lastname: Ferrer
authors.forename: Carmen
authors.initials: C
authors.lastname: Ramírez de Arellano
authors.forename: Gregorio
authors.initials: G
authors.lastname: Asensio
authors.forename: G K Surya
authors.initials: GK
authors.lastname: Prakash