23115-33-5Relevant articles and documents
On the Mechanism of the Baeyer-Villiger Oxidation of Ketones by Bis(trimethylsilyl) Peroxomonosulfate. Intermediacy of Dioxiranes
Camporeale, Michele,Fiorani, Tiziana,Troisi, Luigino,Adam, Waldemar,Curci, Ruggero,Edwards, John O.
, p. 93 - 98 (2007/10/02)
The Baeyer-Villiger oxidation of cyclohexanone (2a) and of acetophenone (2b) by bis(trimethylsilyl)peroxomonosulfate (1) has been reinvestigated using (18)O-labeling techniques.Starting with doubly labeled Me3Si(18)O(18)OSO3SiMe3, mass spectrometric analyses allowed determination of the amount of label appearing in the carbonyl and the OR moiety of the ester (or of the lactone).It has been observed that 2a also promotes the decomposition of 1 to yield oxygen gas, which was analyzed for its (18)O content.Furthermore, ketones 2a, 4-heptanone, and acetone were foundto enhance significantly the rate of oxidation of 1-methylcyclohexene (10) and of trans-β-methylstyrene (13) by 1, yielding 2-methylcyclohexanone (12) and 1-phenylpropanone (15) derived from the isomerization of the initially formed epoxides.These observations, most notably the (18)O-tracer results, point to a mechanism involving the intermediacy of dioxiranes as the prevailing pathway.
