International Summer School PROGRAM - Laboratoire d'Infochimie ...

Novel calixarene- and biscalixarene-based heteroditopic receptors
Ivan Vatsouro, Kirill Puchnin, Boris Bolshchikov, Pavel Zaikin, Maria Logunova,
Vladimir Kovalev
Department of Chemistry, M.V. Lomonosov Moscow State University, Lenin’s Hills,
119991 Moscow, Russia
We present here the results of our research on the novel calix[4]arene-based
heteroditopic host for ion-pair recognition. The hosts of general type 1 are
functionalized calixtubes, which are easily available due to the use of 3-R-1-
adamantylcalix[4]arenes at the step of bis-calixarene preparation. The well established
cation binding site (especially for K +
) formed by eight calixtube oxygens is completed
with two of four urea groups for anion binging thus providing the heteroditopic action
of hosts 1.
Calix[4]arenes bearing one, two or four carboxymethyl groups at narrow rim
reacted with tryptamine or tryptophane methyl ester to give the heteroditopic hosts
through amide formation: the cation binging site is formed by amide oxygens while the
anion binding occurs at the indole NHs. The calixarenes with one or two distal indole
functionalities at narrow rim undergo inter/intramolecular dimerization when kept in
trufluoroacetic acid and then oxidized, thus giving the 2,2’-bisindole-bridged
calix[4]arenes 2 and bis-calix[4]arenes 3. The hosts of type 2 possess the more rigid
cation binding site if compared to their non-dimerized precursors and also the bisindole
fluorophore site for anion recognition.
This research was supported by Russian Foundation for Basic Research, grant
#09-03-00971.