Catalytic oxidation of 4-piperidone-3-carboxylates with manganese(III) acetate in the presence of 1,1-disubstituted alkenes

The manganese(III) acetate-catalyzed cycloperoxidation of 4-piperidone-3-carboxylates with 1,1-disubstituted alkenes is described. The 4-piperidone-3-carboxylates reacted with 1,1-disubstituted alkenes in the presence of a catalytic amount of manganese(III) acetate in air at 23°C to give 1-hydroxy-8-aza-2,3-dioxabicyclo[4.4.0]decane-6-carboxylates in good to moderate yields. The crystal structure of the azabicyclic peroxides was determined by an X-ray single crystal analysis. The oxidation of the 4-piperidone-3-carboxylates with 1,1-diphenylethene using a stoichiometric amount of manganese(III) acetate gave ethenyl- and ethyl-substituted 4-piperidones and 6-hydroxy-3-aza-7-oxabicyclo[4.3.0]nonane-1-carboxylate, which was the same as the product obtained from the hydrogenolysis of the 1-hydroxy-8-aza-2,3-dioxabicyclo[4.4.0]decane-6-carboxylate.