Recent years have witnessed a significant advancement in the field of radical oxidative coupling of ketones towards the synthesis of highly useful synthetic building blocks, such as 1,4-dicarbonyl compounds, and biologically important heterocyclic and carbocyclic compounds. Besides oxidative homo- and cross-coupling of enolates, other powerful methods involving direct C(sp 3)-H functionalizations of ketones have emerged towards the synthesis of 1,4-dicarbonyl compounds. Moreover, direct α-C-H functionalization of ketones has also allowed an efficient access to carbocycles and heterocycles. This review summarizes all these developments made since 2008 in the field of metal-catalyzed/promoted radical-mediated functionalization of ketones at the α-position. 1 Introduction 2 Synthesis of 1,4-Dicarbonyl Compounds 3 Synthesis of Heterocyclic Scaffolds 4 Synthesis of Carbocyclic Scaffolds 5 Conclusion. © Georg Thieme Verlag Stuttgart, New York.