Molecular Acrobatics in Polycyclic Frames: Synthesis of “Kurmanediol” via Post-synthetic Modification of Cage Molecules by Olefinic Metathesis

We report late-stage ring-opening metathesis (ROM), ring-rearrangement metathesis (RRM), and ring-closing metathesis (RCM) approaches to generate expanded pentacycloundecane (PCUD) cage derivatives. These higher-order intricate polycyclic cage systems are aesthetically pleasing and structurally intriguing. Their assembly maintains molecular symmetry during the entire synthetic sequence. To this end, metathesis-based catalysts are used to execute the ROM, RRM, and RCM strategies. The synthetic approach to these cage polycycles involves the Diels–Alder reaction, [2 + 2] photocycloaddition, RRM, ROM, and RCM as key steps.