cyclopropane. An intramolecular nucleophilic attack generates
intermediate F, which should be in an equilibrium with inter-
mediate F¢ via allylic rearrangement. It is understandable that
the intramolecular Friedel–Crafts reaction is favored for the
electron-rich aromatic rings of intermediate F. Thus, there are
two pathways for the intramolecular Friedel–Crafts reaction. For
the diarylvinylidenecyclopropanes 1 bearing moderately electron-
donating groups on the benzene rings or neutral benzene ring (for
example 1a and 1b), the intramolecular Friedel–Crafts reaction
occurs on the aromatic ring of diarylvinylidenecyclopropanes 1 to
give the products 3 since Ar1 and Ar2 are in a larger conjugate
system which can stabilize the cationic intermediate generated in
the Friedel–Crafts reaction to consequently produce the product
3 in a highly stereo- and regioselective manner (Table 1, entries
1, 2 and 8–14 of Table 2, eqn 2). On the other hand, for
the diarylvinylidenecyclopropanes 1 bearing electron-withdrawing
groups on both of the benzene rings, the intramolecular Friedel–
Crafts reaction occurs on the aromatic ring of 5,5-diphenylpenta-
2,3,4-trienoate 2a to generate products 4 (Table 2, entries 3–7)
(Scheme 1).
In conclusion, we have developed novel synthetic methods
for the cascade cycloaddition and Friedel–Crafts reactions of
diarylvinylidenecyclopropanes 1 with ethyl 5,5-diarylpenta-2,3,4-
trienoates 2 to provide a variety of polycyclic esters 3 and 4
in moderate to good yields catalyzed by triflic imide (Tf2NH).
This work is particularly useful to research on the reactivity of
1,2,3-butatriene containing derivatives. Efforts are in progress to
elucidate further mechanistic details of these reactions and to
understand their scope and limitations.
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Acknowledgements
We thank the Shanghai Municipal Committee of Science and
Technology (06XD14005, 08dj1400100-2), National Basic Re-
search Program of China (973)-2009CB825300, and the National
Natural Science Foundation of China for financial support
(20472096, 20872162, 20672127, 20821002 and 20732008) and also
thank Mr. Sun Jie for X-ray diffraction.
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