Aminium
radical cations have been extensively studied as electrophilic
aminating species that readily participate in C–N bond forming
processes with alkenes and arenes. However, their utility in synthesis
has been limited, as their generation required unstable, reactive
starting materials and harsh reaction conditions. Visible-light photoredox
catalysis has emerged as a platform for the mild production of aminium
radical cations from either unfunctionalized or N-functionalized amines. This Perspective covers recent synthetic
methods that rely on the photocatalytic generation of aminium radical
cations for C–N bond formation, specifically in the context
of alkene hydroamination, arene C–H bond amination, and the
mesolytic bond cleavage of alkoxyamines.