Manganese(II and III)-Mediated Synthesis of Cyclic Peroxides from Alkenes, Active Methylene Compounds, and Molecular Oxygen

Article abstract of DOI:10.1246/bcsj.65.1371

The reaction of 1,1-diphenylethene, 1,1-bis(4-chlorophenyl)ethene, 1,1-bis(4-methylphenyl)ethene, 1,1-bis(4-methoxyphenyl)ethene, and 1,1-bis(4-fluorophenyl)ethene with 2-methyl-1,3-cyclohexanedione, 2-methyl-1,3-cyclopentanedione, 2-acetylcyclohexanone, ethyl 2-acetyl-3-oxobutanoate, 3-methyl-2,4-pentanedione, 1,3-cyclohexanedione, and 2,4-pentanedione in the presence of Mn(OAc)2 and molecular oxygen yielded the corresponding cyclic peroxides in moderate-to-good yields.Similar reaction of 1,1-disubstituted alkenes with 1,3-cyclopentanedione in the presence of Mn(OAc)3 and molecular oxygen gave 2,2,9,9-tetraphenyloctahydro-3,4,7,8-tetraoxabenzindene-4a,6a-diols.Acid-catalyzed decomposition of 4-acetyl-6,6-diaryl-3-methyl-1,2-dioxan-3-ols yielded 3-acetyl-5-aryl-2-methylfurans in moderate yields.Treatment of the 4-acetyl-6,6-diaryl-3-methyl-1,2-dioxan-3-ols with alkali gave 6,6-diaryl-3-methyl-1,2-dioxan-3-ols which gave 1-aryl-1,4-pentanediones upon treatment with hydrochloric acid in acetic acid.The synthetic utility and mechanism of the reactions are discussed.