Bicyclic Piperidines <i>via</i> [2 + 2] Photocycloaddition

A synthetic strategy to fused bicyclic piperidinesbuilding blocks for medicinal chemistryis developed. The key step was an intramolecular [2 + 2]-photocyclization. The photochemical step was performed on a gram scale. Crystallographic analysis of the obtained compounds revealed that they occupy a novel chemical space and can be considered as elongated analogues of 3-substituted piperidines.