Issue 24, 2024

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.

Graphical abstract: Copper-catalysed perarylation of cyclopentadiene: synthesis of hexaarylcyclopentadienes

Supplementary files

Article information

Article type
Edge Article
Submitted
14 Apr 2024
Accepted
14 May 2024
First published
16 May 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024,15, 9127-9137

Copper-catalysed perarylation of cyclopentadiene: synthesis of hexaarylcyclopentadienes

Y. Gisbert, P. Simón Marqués, C. Baccini, S. Abid, N. Saffon-Merceron, G. Rapenne and C. Kammerer, Chem. Sci., 2024, 15, 9127 DOI: 10.1039/D4SC02458C

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