The study of the oxidation of 4-methoxyphenethyl phenyl sulfide and 3,4-dimethoxyphenethyl phenyl sulfide with potassium 12-tungstocobalt(III)ate [Co(III)W] suggests that in the radical cations of 3,4,5-(MeO)(3)PhCH2SPh (4) and 2,4,6(MeO)(3)PhCH2SPh (5) the positive charge is not localized on the sulfur atom, but in the benzylic aromatic ring. Nevertheless, in the biomimetic and microsomal oxidation of 4 and 5 the products observed are exclusively sulfoxides and sulfones, which appears in contrast with a mechanism involving the formation of an intermediate sulfide radical cation followed by a fast oxygen rebound. A direct oxygen transfer mechanism seems most likely.
Oxidations of Benzyl and Phenethyl Phenyl Sulfides. Implications for the Mechanism of the Microsomal and Biomimetic Oxidations of Sulfides / Baciocchi, Enrico; Lanzalunga, Osvaldo; Pirozzi, B.. - In: TETRAHEDRON. - ISSN 0040-4020. - 53:(1997), pp. 12287-12298. [10.1016/S0040-4020(97)00560-7]
Oxidations of Benzyl and Phenethyl Phenyl Sulfides. Implications for the Mechanism of the Microsomal and Biomimetic Oxidations of Sulfides
BACIOCCHI, Enrico;LANZALUNGA, Osvaldo;
1997
Abstract
The study of the oxidation of 4-methoxyphenethyl phenyl sulfide and 3,4-dimethoxyphenethyl phenyl sulfide with potassium 12-tungstocobalt(III)ate [Co(III)W] suggests that in the radical cations of 3,4,5-(MeO)(3)PhCH2SPh (4) and 2,4,6(MeO)(3)PhCH2SPh (5) the positive charge is not localized on the sulfur atom, but in the benzylic aromatic ring. Nevertheless, in the biomimetic and microsomal oxidation of 4 and 5 the products observed are exclusively sulfoxides and sulfones, which appears in contrast with a mechanism involving the formation of an intermediate sulfide radical cation followed by a fast oxygen rebound. A direct oxygen transfer mechanism seems most likely.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
