Abstract

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 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

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 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