LAUSR

Aminocatalysis has become a robust and widely used synthetic strategy for the efficient synthesis of valuable molecules. In this context, considerable progress has been achieved in amine‐catalyzed transformations involving radial species, providing new opportunities and platforms for the construction of a broad range of molecules. α‐Iminyl radical cations represent a significant class of reactive species in aminocatalysis and radical reactions, and can be generated through several approaches: single‐electron oxidation of transient enamines via singly occupied molecular orbital (SOMO) activation, conjugate addition of nucleophilic radicals to α,β‐unsaturated iminium ions, and photochemical activation of enamine‐derived electron donor‐acceptor (EDA) complexes. Over the past few decades, a diverse array of valuable and challenging organic transformations driven by α‐iminyl radical cations have been explored. In this review, we aim to highlight important progress in aminocatalyzed reactions involving α‐iminyl radical cations. We will focus on the role of α‐iminyl radical cations and discuss the various types of organic transformations, the mechanism, and the outlook of α‐iminyl radical cation‐driven radical reactions.