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(sp3)-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 during the last decade in the field of metal catalyzed/promoted radical-mediated functionalization of ketones at α-position. |