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Nitroxides, as persistent organic radicals, have found numerous applications in organic synthesis due to their unique redox properties and reactivity. Over the years, a myriad of protocols has been developed using nitroxide to mediate or catalyze various chemical transformations. They have been proven to be an efficient, safe, mild and green alternative to transition metal catalysts. This chapter is intended to provide a comprehensive survey of the diverse applications of nitroxides, including carbon heteroatom oxidations and C–C bond forming reactions, in both homogeneous and heterogeneous catalysis.

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