cycles having a shallow cone 3-fold symmetry structure
bearing all of the potentially useful anchoring groups at
its upper rim.7 Like the calixarenes, CTVs show very
interesting supramolecular properties. However, differ-
ently from the former, their ability to act as cavitands
and form endo-cavity inclusion complexes in solution has
only occasionally been evidenced so far.8 Nevertheless,
examples exist where CTV derivatives have been used
to bind fullerenes and o-carborane in solution,9 although
the role of the π-donor CTV cavity itself remains ques-
tionable.
Syn th esis of Ca vity Exten d ed
Cyclotr iver a tr ylen es
Arturo Arduini, Francesco Calzavacca,
Domenico Demuru, Andrea Pochini,* and Andrea Secchi
Dipartimento di Chimica Organica e Industriale
dell’Universita`, Parco Area delle Scienze 17/ A,
43100 Parma, Italy
andrea.pochini@unipr.it
Received October 21, 2003
It thus appeared us that, despite the very interesting
structural and chemical features of CTVs, only a limited
amount of research on their chemical modification has
been reported so far. In this paper we present a synthetic
study to extend the aromatic cavity of the CTV platform
by using its phenol groups for anchoring three aromatic
moieties and the other three oxygen atoms to increase
the lipophilicity of the receptor.
The design of the new CTV-based hosts was inspired
by our previous results obtained with the heteroditopic
calix[4]arene host3b I that we previously used in the
complexation of tetramethylammonium salts in apolar
media. The four p-hydroxybenzyl substituents present on
the wider rim of I were able to interact with both the
cation and the anion of the tetramethylammonium salts,
through a cooperative effect exerted by the host cavity
and the hydrogen-bond donor ability of the phenol groups,
thus favoring a positive allosteric effect on the ion-pair
recognition (see Figure 1).
Abst r a ct : Aromatic nucleophilic substitution reaction of
cyclotriguaiacylene 1 with fluorobenzene derivatives bearing
electron-withdrawing groups X (CHO, COCH3, CN, NO2) in
the para position gives a series of cyclotriveratrylene deriva-
tives (3a -d ), where the X substituents can be transformed
to hydrogen-bond donor groups to afford new CTV-based
heteroditopic receptors. The substituents of compounds
3a -d favor the facile demethylation reaction of the CTV
derivatives. Attempts to perform alkylation reactions on
derivatives (8c,d ) evidenced the formation of a stereoiso-
meric mixture of symmetrical and unsymmetrical com-
pounds.
An attractive target of supramolecular chemistry1 is
the construction of devices working through molecular
recognition processes. Therefore the synthesis of efficient
and selective receptors having shape and size comple-
mentary with the target guest still represent a field of
current interest. A very convenient strategy for the
construction of efficient hosts is the synthesis of het-
eroditopic receptors starting from a preformed molecular
platform on which to introduce and orient in space
additional binding sites.
During this past decade, we focused our investigations
on the recognition of neutral2 and charged guests2a,3 in
apolar media, through the cavity of several derivatives
of cone conformer calix[4]arene4 having a 4-fold sym-
metry.5 The synthetic approach we followed for the
synthesis of these hosts consists of two main steps:
functionalization of the lower rim to fix the platform in
a rigid cone conformation and then introduction of
suitable additional binding sites at the upper rim. Cy-
clotriveratrilenes6 (CTVs) are intrinsically rigid macro-
(4) For comprehensive reviews on calixarenes see a) Gutsche, C. D.
Calixarenes Revisited - Monographs in Supramolecular Chemistry;
Stoddart, J . F., Ed.; The Royal Society of Chemistry: Cambridge, 1998,
Vol. 6. (b) Calixarenes in Action; Mandolini, L., Ungaro, R., Eds.;
Imperial College Press: London, 2000. (c) Calixarenes 2001; Asfari,
Z., Bo¨hmer, V., Harrowfield, J ., Vicens, J ., Eds.; Kluwer Academic
Publishers: Dordrecht, 2001.
(5) For the complexation of organic guests by other rigid calix[4]-
arene derivatives see also: a) Smirnov, S.; Sidorov, V.; Pinkhassik,
E.; Havlicek, J .; Stibor, I. Supramol. Chem. 1997, 8, 187-196. (b) Orda-
Zgadzaj, M.; Wendel, V.; Fehlinger, M.; Ziemer, B.; Abraham, W. Eur.
J . Org. Chem. 2001, 1549-1561.
(6) (a) Collet, A. In Comprehensive Supramolecular Chemistry;
Atwood, J . L., Davies, J . E. D., McNicol, D. D., Vo¨gtle, F., Eds.;
Pergamon: Oxford, 1996; Vol. 2, pp. 325-365. (b) Collet, A. In
Comprehensive Supramolecular Chemistry; Atwood, J . L., Davies, J .
E. D., McNicol, D. D., Vo¨gtle, F., Eds.; Pergamon: Oxford, 1996; Vol
6, pp 281-303.
(7) The shape of the host cavity can be defined through the angle δ
between the aromatic rings and the plane defined by the bridging
methylene carbons of the hosts. This δ angle is 132° in cyclotrivera-
trylene6 and about 115° in the cone conformer of calix[4]arenes, see
e.g. Arduini, A.; Nachtigall, F. F.; Pochini, A.; Secchi, A.; Ugozzoli, F.
Supramol. Chem. 2000, 12, 273-291.
(1) (a) Schneider, H.-J .; Yatsimirsky, A. Principles and Methods in
Supramolecular Chemistry; J ohn Wiley & Sons Ldt.: Chichester, 2000.
(b) Steed, J . W.; Atwood, J . L. Supramolecular Chemistry; J ohn Wiley
& Sons Ldt.: Chichester, 2000. (c) Comprehensive Supramolecular
Chemistry; Atwood, J . L., Davies, J . E. D., McNicol, D. D., Vo¨gtle, F.,
Eds.; Pergamon: Oxford, 1996. (d) Lehn, J .-M. Supramolecular
Chemistry; VCH: Weinheim, 1995.
(8) See for example: Tanner, M. E.; Knobler, C. B.; Cram, D. J . J .
Org. Chem. 1992, 57, 40-46.
(2) (a) Arduini, A.; McGregor, W. M.; Paganuzzi, D.; Pochini, A.;
Secchi, A.; Ugozzoli, F.; Ungaro, R. J . Chem. Soc., Perkin Trans. 2 1996,
839-846. (b) Arduini, A.; Secchi, A.; Pochini, A. J . Org. Chem. 2000,
65, 9085-9091. (c) Arena, G.; Contino, A.; Magr`ı, A.; Sciotto, D.;
Arduini, A.; Pochini, A.; Secchi, A. Supramol. Chem. 2001, 13, 379-
386. (d) Arduini, A.; Giorgi, G.; Pochini, A.; Secchi, A.; Ugozzoli, F.
Tetrahedron 2001, 57, 2411-2417. (e) Arduini, A.; Brindani, E.; Giorgi,
G.; Pochini, A.; Secchi, A. Tetrahedron 2003, 59, 7587-7594; f) Arena,
G.; Contino, A.; Longo, E.; Spoto, G.; Arduini, A.; Pochini, A.; Secchi,
A.; Massera, C.; Ugozzoli, F. New J . Chem. 2003, in press.
(3) (a) Arduini, A.; Secchi, A.; Pochini, A. Eur. J . Org. Chem. 2000,
2325-2334. (b) Arduini, A.; Giorgi, G.; Pochini, A.; Secchi, A.; Ugozzoli,
F. J . Org. Chem. 2001, 66, 8302-8308. (c) Arduini, A.; Brindani, E.;
Giorgi, G.; Pochini, A.; Secchi, A. J . Org. Chem. 2002, 67, 6188-6194.
(9) (a) Atwood, J . L.; Barnes, M. J .; Burkhalter, R. S.; J unk, P. C.;
Steed, J . W.; Raston, C. L. J . Am. Chem. Soc. 1994, 116, 10346-10347.
(b) Atwood, J . L.; Barnes, M. J .; Gardiner, M. G.; Raston, C. L. Chem.
Commun. 1996, 1449-1450. (c) Blanch, R. J .; Williams, M.; Fallon,
G. D.; Gardiner, M. D.; Kaddour, R.; Raston, C. L. Angew. Chem., Int.
Ed. Engl. 1997, 37, 5504-506. (d) Matsubara, H.; Hasegawa, A.;
Shiwaku, K.; Asano, K.; Takahashi, S.; Yamamoto, K. Chem. Lett.
1998, 923-924. (e) Matsubara, H.; Oguri, S.; Asano, K.; Yamamoto,
K. Chem. Lett. 1999, 431-434. (f) Hardie, M. J .; Godfrey, P. D.; Raston,
C. L. Chem. Eur. J . 1999, 5, 1828-1833. (g) Hardie, M. J .; Raston, C.
L. Angew. Chem., Int. Ed. 2000, 39, 3835-3839. (h) Bond, A. M.; Miao,
W.; Raston, C. L.; Ness, T. J .; Barnes, M. J .; Atwood, J . L. J . Phys.
Chem. 2001, 1687-1695. (i) Hardie, M. J .; Raston, C. L. Cryst. Growth
Des. 2001, 1, 53-58.
10.1021/jo035557m CCC: $27.50 © 2004 American Chemical Society
Published on Web 01/17/2004
1386
J . Org. Chem. 2004, 69, 1386-1388