How to Set the “Chirality” of Polyhedral Small Molecule Hydrocarbons: Decoration and Editing of Cubane Skeleton

Small polyhedral hydrocarbons represented by cubane have attracted attention as potential molecular scaffolds for pharmaceuticals as benzene bioisoster. Cubane is also expected to be used as a chiral scaffold, but due to its high symmetry, it is necessary to introduce chirality by sequential site‐selective introduction of substituents. Furthermore, polyhedral desymmetrized isomers of cubane, such as cuneane and semibullvalene, and extended cage compounds, such as bishomocubane and homocuneane, exhibit chirality and are also expected to be used as new optically active scaffolds. In this concept, we would like to explain the synthetic routes we have planned, specifically, the decoration and editing of the cubane skeleton. In this Concept, we introduce chirality via substituent introduction to cubane and discuss the synthesis associated with imparting chirality to polyhedral hydrocarbons like cuneane, semibullvalene, bishomocubane and homocuneane using “Scaffold‐editing” method, thereby highlighting the future possibilities in this field of research.