Distonic Radical Cations in Visible‐Light‐Driven Cycloadditions

The advent of photoredox catalysis has created a massive buzz in the field of synthetic organic chemistry. As the photoredox process is invariably mediated by the transfer of single electrons, species such as radical cations are inevitable. These species have orcastracized various synthetic transformations that otherwise would have been difficult to achieve. One such class of transformations is the cycloaddition reaction. For driving such reactions, it is often necessary that the radical and cation sites are present on different atoms, in other words, are distal or “ distonic” in nature. In the present review, the development of distonic radical cations has been brought forth and their tactical exploitation over the years for the purpose of cycloaddition reactions in the visible‐light realm. The entirety of the manuscript has been divided into categories discussing [2 + 2], [3 + 2], and [4 + 2] cycloadditions. In each case, the distonic radical cation that drives the cycloaddition has been highlighted along with necessary discussions, providing readers with an opportunity to appreciate the power of these wonderful intermediates.