Copper-catalysed perarylation of cyclopentadiene: synthesis of hexaarylcyclopentadienes

Abstract

While hexaphenylsilacyclopentadiene (hexaphenylsilole) is viewed as an archetypal Aggregation-Induced Emission (AIE) luminogen, its isostructural hydrocarbon surrogate hexaphenylcyclopentadiene has strikingly never been investigated in this context, most probably due to a lack of synthetic availability. Herein, we report a straightforward synthesis of hexaphenylcyclopentadiene, via the direct perarylation of cyclopentadiene upon copper(I) catalysis under microwave activation, with the formation of six new C–C bonds in a single synthetic operation. Using zirconocene dichloride as a convenient source of cyclopentadiene and a variety of aryl iodides as coupling partners, this copper-catalysed cross-coupling reaction gave rise to a series of unprecedented hexaarylcyclopentadienes. The latter are direct precursors of extended π-conjugated polycyclic compounds, and their cyclodehydrogenation under Scholl reaction conditions yielded helicenic 17,17-diarylcyclopenta[l,l′]diphenanthrenes. These structurally complex polyannelated fluorene derivatives can now be prepared in only two synthetic steps from cyclopentadiene.