SCHEME 1
Short and Efficient Synthesis of Coronene
Derivatives via Ruthenium-Catalyzed
Benzannulation Protocol
Hung-Chin Shen, Jhih-Meng Tang, Hsu-Kai Chang,
Chia-Wei Yang, and Rai-Shung Liu*
Department of Chemistry, National Tsing-Hua University,
Hsinchu, Taiwan, ROC 30043
Received June 19, 2005
dures and inefficiency,6 typically including a pyrolysis
step at high temperatures. Only persulfurated coronene
derivatives were prepared directly from perchlorocoro-
nene.7 The lack of a convenient and efficient synthesis
of coronenes impedes their progress in organic chemistry.
Scott and co-workers8 proposed a short synthesis of
coronenes from metal-catalyzed cyclization of bis(1,1-
ethynyl)alkene species, which was prepared conveniently
in three steps from commercially available anthraquino-
ne (Scheme 1, eq 2). This approach was, however,
inefficient as it gave coronene in only 15-20% yield using
20 mol % RuPPh3(cymene)Cl2 catalyst; no additional
coronene example was reported from the use of this
catalytic approach. In this study, we sought to accomplish
this catalytic transformation using TpRuPPh3(CH3-
CN)2PF6 catalyst.9 This cationic species readily reacts
with terminal alkynes to afford highly electrophilic
ruthenium-vinylidenium intermediates and enables the
realization of many interesting catalytic cyclizations.9
TpRuPPh3(CH3CN)2PF6 (3 mol %) was very active in cata-
lytic benzannulation of 1-phenyl-2-ethynylbenzenes in dichlo-
roethane (60 °C, 36 h) to afford phenanthrene in 95% yield.
This method is applicable to the synthesis of various
polycyclic aromatic hydrocarbons via two- and four-fold
benzannulations, including various substituted coronene
derivatives (53-86% yields) using this catalyst at a moderate
loading (10 mol %).
Large polycyclic aromatic compounds such as hexa-
benzocoronene derivatives1-3 (Scheme 1, eq 1) tend to
form columnar liquid crystal mesophases via intermo-
lecular π-π stacking. This structural feature shows
promising applications for organic transistors4 and pho-
tovoltaic devices.5 The facile and practical synthesis of
hexabenzocoronene derivatives,1-3 notably by the work
of Mu¨llen and co-workers, enhances the development of
these materials for optoelectronic applications.4,5 In
contrast with hexabenzocoronenes, published methods for
the synthesis of coronenes are plagued with long proce-
Catalytic transformations of 3,5-dien-1-ynes, 4-phenyl-
3-en-1-ynes, and 1-phenyl-2-ethynylbenzenes into ben-
zene derivatives have been studied by either chemical
oxidation10 or metal-catalyzed cyclization (Scheme 2).11-13
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10.1021/jo0512599 CCC: $30.25 © 2005 American Chemical Society
Published on Web 10/21/2005
J. Org. Chem. 2005, 70, 10113-10116
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