Oxidation of methylcyclohexanols by the Pb(OAc)4-LiCl system

1. In the reaction of 2-, 3-, and 4-methylcyclohexanols with the Pb(OAc)4,-LiCl oxidizing system, methylcyclohexylalkoxyl radicals are generated, and their formation was confirmed by EPR with the use of a spin trap. 2. The 2- and 4-methylcyclohexylalkoxyl radicals are regioselectively rearranged into 1-methyl- and 3-methyl-5-formylamyl radicals, and the 3-methylcyclohexylalkoxyl radical decomposes in two directions, yielding 2-methyl- and 4-methyl-5-forraylarayl radicals. In the Pb(OAc)4-LiCl system, these radicals are quantitatively oxidized into chloroalkanals. 3. The trans-2 and cis-3-methylcyclohexanols exhibit higher reactivity with respect to the Pb(OAc)4-LiCl system than cis-2 and trans-3-methylcyclohexanols. The reactivity of both isomers of 4-methylcyclohexanol is the same.