Oxygen-bearing structures are attractive synthetic targets due to their wide presence in a great number of natural products and biologically active molecules, and their role as useful synthons in organic synthesis. Thus, the preparation of O-bearing compounds has been an important topic. Transition metal-catalyzed aerobic oxygenation strategy has emerged as a novel and efficient methodology for constructing C-C bonds and C-heteroatom bonds. This strategy has become one of the most important and useful synthetic method in organic synthesis of O-bearing compounds. Based on the previous work of our group and others, herein, the new applications of transition metal-catalyzed oxygenation of C-H bond activation and C-C bond cleavage with oxygen as oxygen source are discussed. The recent progress in trans-metal catalytic oxygen insertion of ketones, aldehydes, alkene, alkynes, arene and aromatic heterocyclic compounds has been reviewed. Transition metal-catalysts can initiate oxygen insertion reaction of free radical pathway and realize selective insertion of oxygen radicals under oxygen oxidation. These reactions are characterized by mild conditions, environmental protection and highly atom economy.

Key words: transition metal catalysis, oxygen oxidation, C-H activation, C-C cleavage, oxygenated reaction, radical pathway