Stereochemistry of the C-S bond cleavage in cis-2-methylcyclopentyl phenyl sulfoxide radical cation.
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.
Baciocchi
Enrico
E
Dipartimento di Chimica and Istituto CNR di Metodologie Chimiche-IMC, Sezione Meccanismi di Reazione c/o Dipartimento di Chimica, Sapienza Universita di Roma, P.le A. Moro 5, 00185 Rome, Italy.
Lanzalunga
Osvaldo
O
Lapi
Andrea
A
Maggini
Laura
L
D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D003517:Cyclopentanes / Q000737:chemistry*; D010084:Oxidation-Reduction; D010782:Photolysis; D013237:Stereoisomerism; D013454:Sulfoxides / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*; D014025:Titanium / Q000737:chemistry
D003517:Cyclopentanes; D013454:Sulfoxides; C539731:cis-2-methylcyclopentyl phenyl sulfoxide; C009495:titanium dioxide; D013455:Sulfur; D002244:Carbon; D014025:Titanium