| 19146449 |
Baciocchi E, Lanzalunga O, Lapi A, Maggini L: Stereochemistry of the C-S bond cleavage in cis-2-methylcyclopentyl phenyl sulfoxide radical cation. J Org Chem. 2009 Feb 20;74(4):1805-8.
The TiO (2) photocatalyzed oxidation of cis-2-methylcyclopentyl phenyl sulfoxide in the presence of Ag (2) SO (4) in MeCN/H (2) O 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 H (2) O and MeCN. Attack of H (2) O on the ion radical pair may also occur, but as a minor route (<3%), with formation of trans-2-methylcyclopentanol. |
112(1,2,2,2) |