Synthesis of diamondoids through hydrogenation of adamantane-annulated arenes

Abstract Diamondoids are cage-shaped saturated hydrocarbons whose carbon scaffolds are substructures of diamond. Despite their potential application, the availability of diamondoids has been significantly limited due mainly to the difficulty in synthesis. Herein, we report a new synthetic methodology for diamondoids. It was found that adamantane-annulated arenes, which can be synthesized by our recently developed method, can be transformed to saturated hydrocarbons by catalytic hydrogenation of arene moieties. The thus-obtained hydrocarbons are unnatural diamondoids, which are otherwise difficult toobtaine. The structural analysis and DFT calculation of the reaction mechanism were also performed to initiate exploration of the untapped synthetic chemistry of diamondoids.