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[2.2]Paracyclophane is the prototypical layered hydrocarbon and has been essential for investigations of through-space electronic interactions. Over the last years more examples of tetrasubstituted derivatives have been reported. This minireview discusses the synthetic approaches towards various substitution patterns and provides a survey over different approaches used to achieve and derivatize symmetric tetrasubstitution. The first two sections of this work present homo-tetrasubstituted derivatives, while the third section gives insight into symmetrically hetero-tetrasubstituted analogues. These approaches are briefly discussed, the resulting structures are presented in detail, and their specific properties resulting from the incorporation of [2.2]paracyclophane are elucidated.