6533b82cfe1ef96bd128fe6b
RESEARCH PRODUCT
Oxyfunctionalization of Aliphatic Esters by Methyl(trifluoromethyl)dioxirane
And Rossella MelloGloria CastellanoGregorio AsensioM. E. González Núñezsubject
chemistry.chemical_classificationReaction ratechemistry.chemical_compoundTrifluoromethylHydrocarbonchemistryDioxiraneBicyclic moleculeOrganic ChemistryMoietyMethyleneSelectivityMedicinal chemistrydescription
The oxidation of lineal, cyclic, and bicyclic aliphatic p-chlorobenzoic and p-chorobenzenesulfonic acid esters 2 with methyl(trifluoromethyl)dioxirane (TFDO) (1) occurs at positions in the hydrocarbon chain distant from the directing group with a significant degree of selectivity to give the corresponding keto or hydroxy esters. Compounds 2 are relatively deactivated with respect to this oxidation due to the electron-withdrawing nature of the ester moiety. Methylene Cα−H and Cβ−H bonds remain unchanged in all cases, but tertiary Cβ−H bonds undergo oxidation with TFDO (1). Stereoelectronic factors are used to explain the faster reaction rate in competition experiments for the oxidation of endo-norbornyl ester 2h than for its exo-isomer 2g.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 1996-01-01 | The Journal of Organic Chemistry |