In the context of Tröger base chemistry, regio- and stereoselective Csp3−H azidation reactions are reported. Azide functional groups are introduced at either one or the two benzylic positions selectively. Mild conditions and good yields are afforded by the combination of TMSN3 and iodosobenzene PhIO. The process occurs with high enantiospecificity (es 96–99 %) and—interestingly and importantly—via bridgehead iminium intermediates as shown by mechanistic and in-silico studies. Finally, mono- and bistriazole derivatives were prepared in high yields and enantiospecificity by using copper-catalyzed alkyne azide cycloaddition (CuAAC) reactions; some of the products were used as anion-binding organocatalysts for the tritylation of amines and alcohols.