Radical additions to C=N bonds offer potential for efficient access to multifunctional chiral building blocks under mild conditions. Utilization of these additions from tethered radicals toward the synthesis of naturally occurring compounds has been studied. Extension of stereocontrol models to 6-exo radical cyclizations with imino acceptors remains an open question. Methods have been developed for 6-exo cyclization using alkyl and vinyl radicals. Synthetic approaches to naturally occurring aminosugras have given further insights into the reactivity and selectivity of these 6-exo cyclizations.