Mechanism of the oxidation of sulfides by dioxiranes: conformational mobility and transannular interaction in the oxidation of thianthrene 5-oxide.
The detailed study of the oxidation of thianthrene 5-oxide (1) with methyl(trifluoromethyl)dioxirane (5b) in different solvents and in the presence of (18)O isotopic tracers is reported. Thianthrene 5-oxide (1) is a flexible molecule in solution, and this property allows for transannular interaction of the sulfoxide group with the expected zwitterionic 7 and hypervalent 10-S-4 sulfurane 9 intermediates formed in the oxidation and biases the course of the reaction toward the monooxygenation pathway.
González-Núñez
María Elena
ME
Departamento de Química Orgánica, Universidad de Valencia, Avda. V. Andrés Estellés s/n, 46100-Burjassot (Valencia), Spain.
Mello
Rossella
R
Royo
Jorge
J
Asensio
Gregorio
G
Monzó
Isidro
I
Tomás
Francisco
F
López
Jesús García
JG
Ortiz
Fernando López
FL