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Skeletal rearrangement of all-carbon spiro skeletons mediated

by a Lewis acidw
Fei Zhao,a Chao Wang,a Lantao Liu,ab Wen-Xiong Zhanga and Zhenfeng Xi*ac
Received (in Cambridge, UK) 20th July 2009, Accepted 21st August 2009
First published as an Advance Article on the web 11th September 2009
DOI: 10.1039/b914619a

Mediated by AlCl3, substituted spiro[4.5]deca-tetraenes under-

went novel and selective skeletal rearrangement to generate
indene derivatives in high to excellent yields.
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Selective carbon–carbon bond1 and carbon–hydrogen bond2

cleavage reactions are of great importance both fundamentally
and practically. Achievements in these areas have been much
more realized in a wide variety of functionalized or highly Scheme 1 Cleavage of C–C and C–H bonds in all-carbon spiro
active compounds than in those unfunctionalized or thermo- compounds.
dynamically stable systems, probably due to the extreme
difficulty to cut C–C or C–H bonds without any mediation (path B, Scheme 2), implying the reaction of both spiro
or facilitation by active substituents or special structures. For compounds 1a and 1a 0 may have similar reaction pathways
example, there are many reports on breaking C–C bonds in leading to the indene derivative mediated by AlCl3. Employing
small rings;3,4 reports also appeared on the cleavage of C–C directly a mixture of 1a and 1a 0 as starting materials under the
bonds in cyclopentadienyl ligands in metallocenes5,6 or above condition again afforded the same indene derivative 2a
aromatic compounds,7 whereas research on the cleavage of as the only product in 80% isolated yield (path C, Scheme 2).z
C–C bonds in those all-carbon medium cyclic compounds In situ NMR experiment demonstrated that 2a was formed in
has been very rare in the literature,1 although interesting the reaction mixture before quenching and work-up.
transformations, surprising mechanisms, or synthetically Consequently, as listed in Table 1, spiro compounds 1b–1e,
useful protocols can be expected from these reactions. As and 1b 0 –1e 0 could be transformed into the corresponding
our continuous interest in cleavage and synthetic applications indene derivatives 2b–2e or 2c 0 in good to excellent isolated
of unactivated chemical bonds6,8,9, we would like to report yields following the procedure as described above. It is noticeable
herein our preliminary results on Lewis acid10 mediated that a mixture of 1b and 1b 0 afforded 2b as the sole product,
skeletal rearrange-ment of all-carbon cyclic compounds whilst a mixture of 1c and 1c 0 gave two isomeric products 2c
spiro[4.5]deca-tetraene 1 or 1 0 yielding indene derivatives 211 and 2c 0 in 73% combined isolated yield. These results are
via sequential cleavage of both C–C and C–H bonds informative for the skeletal rearrangement mechanisms.
(Scheme 1). Notably, different from the strained spiro As a fundamental reaction in organic chemistry, the
compounds,12 in our results the inert sp2–sp3 C–C bond of reaction of Lewis acids such as AlCl3, which have an
the stable cyclopentadiene moiety was cleaved under mild electron-deficient nature, with CQC double bond would result
conditions. To the best of our knowledge, this is the first in the formation of reactive carbon cation species.10 Thus, for
example of such skeletal rearrangements. the skeletal rearrangement of spiro compounds 1 or 1 0 to
All-carbon spiro compounds 1 and 1 0 could be readily indene derivatives 2, a proposed mechanism including
prepared in high yields from 1-lithio-4-aryl-1,3-butadienes.13,14 intermediacy of carbon cation species is exhibited in Scheme 3.
Treatment of 1a with 1 equivalent of AlCl3 in CH2Cl2 resulted The intermediate 3, formed through the CQC bond in the six-
in the formation of an indene derivative 2a15 in 92% isolated membered ring of 1 coordinating to AlCl3,16 would trigger an
yield (path A, Scheme 2), while a similar procedure using 1a 0
produced the same indene derivative 2a in 71% isolated yield

a
Beijing National Laboratory for Molecular Sciences (BNLMS),
Key Laboratory of Bioorganic Chemistry and Molecular Engineering
of Ministry of Education, College of Chemistry, Peking University,
Beijing 100871, China. E-mail: [email protected];
Fax: +86 10 62751708; Tel: +86 10 62759728
b
Institute of Chemistry, Chinese Academy of Sciences, Beijing,
100190, China
c
State Key Laboratory of Organometallic Chemistry, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences,
Shanghai, 200032, China
w Electronic supplementary information (ESI) available: Experimental
details and scanned NMR spectra of all new products. See DOI:
10.1039/b914619a Scheme 2 AlCl3-Mediated formation of indene 2a from 1a and 1a 0 .

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Table 1 Synthesis of indene derivatives 2 from spiro compounds 1

Entry 1 and 1 0 (ratio of 1:1 0 ) Indene 2

1
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Scheme 3 A proposed mechanism.

Scheme 4 Two reaction pathways of cyclization of 5c.

mechanism, but also provide an alternative route to synthesize

indene derivatives.
4 In summary, we have reported in this paper a facile and
efficient Lewis-acid-mediated skeletal rearrangement of
unstrained spiro[4.5]deca-tetraene to generate indene derivates
via tandem cleavage of allylic C–H and inert C–C bonds.
Further investigation on the mechanism, scope and applications
are in process.
intramolecular proton transfer via ring-openning process and
aromatization of 4, to give the diene 5. In succession, with the
Table 2 Synthesis of indene derivatives 2 from 5
existance of Lewis acid, an intramolecular Friedel–Crafts
reaction of 5 would herein take place and afford 2 as the final
product. Indeed, diene 5 was observed during utilizing in situ
NMR to track the reaction. According to this mechanism, it is
quite reasonable that in the case of 1c and 1c 0 , 2c and 2c 0 were
obtained as a mixture via cyclization of 5c with different
regio-selectivity (Scheme 4). Although this result is helpful
for testifying the possibility of the above mechanism, yet other
reaction pathways still can not be ruled out (see supporting
informationw). Diene 5 Ar Indene 2 (isolated yield)
In order to get further evidence in support of the above 5a Ph 2a (85%)
proposed reaction mechanisms, we began to investigate the 5b 2 0 -Tolyl 2b (60%)
5c 3 0 -Tolyl 2c + 2c 0 (total 78%, 6:4)
reaction between dienes 513a and AlCl3. As shown in Table 2,
treated with AlCl3, dienes 5a–5d could be converted into
2a–2c, 2c 0 or 2f in good to excellent yield. It is worth
emphasizing that the ratio of 2c and 2c 0 acquired from 5c is 5d 4 0 -Tolyl
completely identical with the one from reaction of 1c and 1c 0 ,
which can be explained as the dicussion above (Scheme 4).
Hence, these results not only support the above propounded

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This work was supported by the National Natural Science 4 (a) For recent examples on C–C bond cleavage in four-memdered
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