Halonium ion-mediated reaction of unsaturated hydroperoxy acetals. Competition between the formation of cyclic peroxides and the migration of the methoxy (or hydroxy) group.
Monoozonolyses of dienes 2 in methanol gave in each case the corresponding unsaturated alpha-methoxy hydroperoxides 3. Capture of 2-alkyl-substituted cyclohexanone oxides by methanol was highly diastereoselective, thereby providing exclusively the hydroperoxides derived from attack by methanol from the less hindered face of the carbonyl oxide intermediates. Halonium ion-mediated reactions of the hydroperoxides 3 gave the novel methoxy- or hydroxy-migrated products, together with the expected halogen-substituted 1, 2-dioxanes and/or 1,2-dioxepanes, the composition of the product mixture being a function of the halogenating agent utilized and the structure of 3.
Tokuyasu
T
T
Department of Materials Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565, Japan.
Masuyama
A
A
Nojima
M
M
McCullough
K J
KJ
D000080:Acetals / Q000138:chemical synthesis* / Q000737:chemistry; D000962:Antimalarials / Q000138:chemical synthesis* / Q000737:chemistry; D003500:Cyclization; D004146:Dioxanes / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D000432:Methanol / Q000378:metabolism; D008958:Models, Molecular; D010545:Peroxides / Q000138:chemical synthesis* / Q000737:chemistry
D000080:Acetals; D000962:Antimalarials; D004146:Dioxanes; D010545:Peroxides; D000432:Methanol