Accessing the Synthetic Chemistry of Radical Ions

Organic reactions involving radical cation and radical anion intermediates are synthetically powerful umpolung processes that enable electronically mismatched couplings between pairs of electron-rich or pairs of electron-poor organic fragments. Nevertheless, the adoption of these reactions as synthetic methods has been relatively slow in comparison with that of reactions involving more conventional reactive intermediates such as carbanions, carbocations, and neutral radicals. This Microreview provides a brief survey of radical ion chemistry and highlights the use of transition metal photocatalysis as a convenient means to investigate radical-ion-mediated transformations.