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Thiacalix[4]arenes with triple bonds on the lower rim : synthesis
and reactivity.
N.A. Epifanova a , E.V.Popova a , S.V. Kharlamov a , Sh.K. Latipov a , S.F. Vasilevsky
b
a
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b , S.E. Solovieva a , I.S. Antipin a .
A.E. Arbuzov Institute of Organic and Physical Chemistry KazCS RAS, Russia,
420088, Kazan, Arbuzov str. 8. E-mail:
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O-CH2-C CH
OCH2C C
R1 1 2 3
epifanova@iopc.ru
Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian
Academy of Sciences, 630090, Novosibirsk, Russian Federation.
(Thia)calix[4]arenes are useful platforms for obtaining of three-dimensional
structures – building blocks for construction of supramolecular systems. They are well-
known as molecular receptors for bounding of different type guests: metal ions, organic
substrates and metal complexes. Multiple bonds make (thia)calix[4]arene able to form
“click-chemistry” products, which could be used for making of new generation
biologically active compounds, selective complexing agents and building blocks for
obtaining of metal-organic structures (MOF’s), probes for biomedical applications.
In the present work alkylation reactions thiacalix[4]arenes by propargyl bromide
in the presence of alkali metal carbonates were systematically studied. Regularity of
different stereoisomeric forms formation in dependence of used base nature were
established. It was shown, that classical alkylation with using of propargyl bromide
gives the possibility to obtain tert-butyl-thiacalix[4]arene and thiacalix[4]arene
derivatives (1) with triple bonds at the lower rim in different conformations in one step.
(Thia)calix[4]arenes with propargyl groups were used in Sonogashira cross-
coupling (2) as well as in“click-chemistry” (3) reactions.
Structure and stereoisomeric forms of new compounds were characterized with the use
of 1D and 2D NMR, IR spectroscopy and mass-spectrometry.
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The work was supported by the Russian Foundation for Basic Research (grant no. 10-
03-00728).