K. Hegemann et al., REGIOSELECTIVITY OF OXYSULFENYLATIONS OF CYCLOOCTA-1,5-DIENE, Journal fur praktische Chemie, Chemiker-Zeitung, 340(5), 1998, pp. 455-458
The regioselectivity of transannular O-hetero-cyclization of cycloocta
-1,5-diene (1) with phenylsulfenyl chloride and methanol or water, res
pectively, is determined by the oxy-component which acts as nucleophil
ic partner in the electrophilic three component reaction. The thermody
namically more stable endo, -2,6-bis(phenylsulfenyl)-9-oxabicyclo[3.3.
1]nonane (2) is formed almost exclusively in methanol while the isomer
ic 9-oxabicyclo[4.2.1]nonane (3) is favored under kinetic control in t
he presence of water. The oxidation of 2 or 3 yields the bissulfones 4
and 5, respectively.