Substituent effect on the photochemistry of 4,4-dialkoxylated- and 4-hydroxylated cyclohexenones

Photochemistry of the title compounds in various solvents was studied using a broad band of light centered at 350 nm. C-4 spiroketal cyclohexenone 4 (1.0 M) afforded dimers and 12b with the predominance of the former in polar solvent and the latter in nonpolar solvent. When the concentration was reduced to, 4 underwent solvent addition in nonpolar solvent and ring-contraction in polar solvents. 4,4-Dimethoxycyclohexenones 5a–d in TFE exhibited a different photochemical behavior. The 5-vinyl-substituted enone afforded the bridged-bicyclic ketone 16. Cyclohexenone 5b with methyl moieties at C-2 and C-3 underwent aromatization whereas cyclohexenones with butyl substituent at C-5 and 5d with silylated alcohol at C-2 underwent solvent exchange. In γ-hydroxylated cyclohexenones 6a–c ring-contraction and solvent exchange were observed. Photochemistry of the title compounds from the mechanistic viewpoint is also described.