Dynamic Kinetic Activation of Aziridines to Access Azepines

The activation of aziridines is typically a substrate-controlled process, where the regioselectivity of C–N bond cleavage is strongly influenced by the substitution pattern on the aziridine ring. Recently, our group developed a dynamic kinetic protocol that enables a catalyst-controlled activation strategy for aziridines. This article first provides a brief overview of existing methods for aziridine activation and then focuses on the development of a radical–polar crossover (4+3) cycloaddition between aziridines and 2-substituted 1,3-dienes, which is made possible through this dynamic kinetic activation approach.