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