The TiO(2) photocatalyzed oxidation of cis-2-methylcyclo-pentyl 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
Stereochemistry of the C-S Bond Cleavage in cis-2-Methylcyclopentyl Phenyl Sulfoxide Radical Cation / Baciocchi, Enrico; Lanzalunga, Osvaldo; Lapi, Andrea; Maggini, L.. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 0022-3263. - 74:(2009), pp. 1805-1808. [10.1021/jo802619y]
Stereochemistry of the C-S Bond Cleavage in cis-2-Methylcyclopentyl Phenyl Sulfoxide Radical Cation
BACIOCCHI, Enrico;LANZALUNGA, Osvaldo;LAPI, Andrea;
2009
Abstract
The TiO(2) photocatalyzed oxidation of cis-2-methylcyclo-pentyl 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-methylcyclopentanolI documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.