Achieving Olympicene Functionalization Three Ways

Polycyclic aromatic hydrocarbons (PAHs) and their derivatives are of interest in many fields, from materials science to supramolecular chemistry. 6<i>H</i>-Benzo[<i>cd</i>]pyrene, or olympicene, is a PAH bearing a central <i>sp</i>³-carbon bridge. We sought methods to modify this center position while maintaining stable tetrahedral geometry. Here, we characterize reactivity patterns of three olympicene core starting materials, with two of the three leading to center functionalization of the olympicene core, including the first use of 5<i>H</i>-benzo[<i>cd</i>]pyren-5-one as an olympicene synthon.