Catalytic Oxidations with Meta-Chloroperoxybenzoic Acid (m-CPBA) and Mono- and Polynuclear Complexes of Nickel: A Mechanistic Outlook

Selective catalytic functionalization of organic substrates using peroxides as terminal oxidants remains a challenge in modern chemistry. The high complexity of interactions between metal catalysts and organic peroxide compounds complicates the targeted construction of efficient catalytic systems. Among the members of the peroxide family, m-chloroperoxybenzoic acid (m-CPBA) exhibits quite complex behavior, where numerous reactive species could be formed upon reaction with a metal complex catalyst. Although m-CPBA finds plenty of applications in fine organic synthesis and catalysis, the factors that discriminate its decomposition routes under catalytic conditions are still poorly understood. The present review covers the advances in catalytic C–H oxidation and olefine epoxidation with m-CPBA catalyzed by mono- and polynuclear complexes of nickel, a cheap and abundant first-row transition metal. The reaction mechanisms are critically discussed, with special attention to the O–O bond splitting route. Selectivity parameters using recognized model hydrocarbon substrates are summarized and important factors that could improve further catalytic studies are outlined.