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Organic synthesis using carbon centred radicals generated by one electron oxidants is of current interest. Although Mn(OAc)3 has received the most attention, it appears that cerium(IV) ammonium nitrate (CAN) would be a very useful reagent for the generation of radicals. The recent application of CAN in the construction of C–C bonds are highlighted in this review. CAN has been shown to mediate the facile oxidative addition of 1,3-dicarbonyl compounds to activated and unactivated alkenes leading to dihydrofurans and furanones. In most cases the reactions occur under milder conditions and the yields are superior when compared to Mn(OAc)3 mediated reactions. The results available thus far suggest that CAN offers cast potential in radical mediated organic synthesis.