The formation of byproducts during the Co(acac)(2) and Cr(acac)(3)-catalyzed cyclohexane autoxidation is compared with the noncatalyzed thermal process. Coll ions seem to cause only a moderate perturbation of the reaction mechanism, causing a fast conversion of the cyclohexyl hydroperoxide via a redox cycle, rather than via abstraction of the alpha H-atom by chain carrying peroxyl radicals. Nevertheless, both the radical propagation and the Co-II-induced decomposition of the hydroperoxide cause the formation of cyclohexoxy radicals that are partially transformed to 6-hydroxyhexanoic acid, the major primary byproduct for these systems. However, during the Co-II-catalyzed reaction, the concentration of cyclohexanone increases much faster than that of the hydroperoxide, causing the ketone to take over the role of dominant byproduct source. A mechanism for the conversion of cyclohexanone to ring-opened byproducts is put forward. Cr(acac)(3) seems to catalyze additional reactions, some of them probably leading directly to byproducts. Indeed, the evolution of (by)products is significantly different from the Co-II-catalyzed and the thermal systems, in the sense that they all seem to be primary in origin.