Efficient and Modular Synthesis of New Structurally Diverse Functionalized [n]Paracyclophanes by a Ring‐Distortion Strategy

With the goal of synthesizing new n]paracyclophanes, the expansion of the scope of a strategy originally disclosed by Winterfeldt et al., was investigated. This approach involves sequential Diels–Alder/retro‐Diels–Alder reactions, the applications of which have been constrained so far to steroid derivatives. An efficient access to new functionalized 9]‐, 10]‐, and 16]paracyclophanes, including original cage architectures, was developed from readily available building blocks using thermal electrocyclization and a cycloaddition/cycloreversion sequence as the key steps.