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Stereochemistry of the C−S Bond Cleavage in cis-2-Methylcyclopentyl Phenyl Sulfoxide Radical Cation

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journal contribution
posted on 2009-02-20, 00:00 authored by Enrico Baciocchi, Osvaldo Lanzalunga, Andrea Lapi, Laura Maggini
The TiO2 photocatalyzed oxidation of cis-2-methylcyclopentyl phenyl sulfoxide in the presence of Ag2SO4 in MeCN/H2O leads to the formation of 1-methylcyclopentanol, 1-methylcyclopentyl acetamide, and phenyl benzenethiosulfonate as the main reaction products. It is suggested that the C−S heterolysis in the radical cation is an unimolecular process leading to an ion radical pair. Fast 1,2-hydride shift in the secondary carbocation leads to 1-methylcyclopentyl carbocation that forms the observed products by reaction with H2O and MeCN. Attack of H2O on the ion radical pair may also occur, but as a minor route (<3%), with formation of trans-2-methylcyclopentanol.