Two approaches to the synthesis of functionalized bridged bicyclic sulfonamides with a bridgehead nitrogen atom were developed. The target compounds were obtained either by introduction of a CH2SO2 bridge into functionalized monocyclic substrates or by final‐step carboxylation of parent bicyclic cores. The described methods allowed preparation of the final products on a multigram scale.

Azido-Perylenediimide N3-PDI was isolated as a stable solid which readily converts into N-annulated PDI in solution only when exposed to visible light. N3-PDI was also engaged into CuAAC reactions with...