4th EucheMs chemistry congress

Poster Session 1
s1035
chem. Listy 106, s587–s1425 (2012)
Poster session 1 - organic chemistry
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SyntheSiS of Steroid-triLoBoLide CLiCKAteS
for BioLoGiCAL StudieS
M. JuráSeK 1 , P. drASAr 1 , J. hArMAthA 2
1 Institute of Chemical Technology in Prague, Chemistry of
Natural Compounds, Prague 6, Czech Republic
2 Institute of Organic Chemistry and Biochemistry, Chemistry of
Natural Compounds, Prague 6, Czech Republic
In this contribution synthesis of short series of conjugated
natural products concerned to steroids and trilobolide (TB) is
described. Trilobolide is a sesquiterpene lactone which was
previously found to have an inhibition activity of
sarco/endoplasmic reticulum Ca2+ -ATPase (SERCA). Also, it
has been demonstrated that TB can serve as an
immunostimulatory agent. Estradiol, testosterone, pregnendiol
and dihydroxyandrosten were used as motive of steroidal
moiety. These steroids as relatively lipophilic compounds may
modify its biological availability and transport, moreover,
fundamental steroidal skeletons are recognized by nuclear
receptors in the nucleus of the cell. In this work TB is transformed
at C-6 position to 5-azidovalerate. This structure serve as a
building block for successive click reaction with ethynylated
steroids. For comparison, steroids were also clicked with
5-azidovaleric acid to give corresponding trilobolide attached
moieties. These compounds are now given for biological screens
and tests to give new information about general behavior of such
compounds.
Keywords: trilobolide; steroids; click chemistry;
4 th EucheMs chemistry congress
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Anion BindinG ProPertieS of A SALoPhen zinC
CheLAte / BiLe ACid ConJuGAte inCorPorAted
into CtABr MiCeLLeS
o. JurCeK 1 , M. CAMetti 2 , e. KoLehMAinen 1 ,
K. riSSAnen 1
1 University of Jyväskylä, Department of Chemistry, Jyväskylä,
Finland
2 Politecnico di Milano, Department of Chemistry, Milano, Italy
Metal complexes are excellent Lewis acidic binding sites for
anions. In particular, Salophen-Metal complexes are extensively
studied species, which have been successfully employed as
receptors, catalysts, and carriers. [1] Bile acids are amphiphilic
molecules found in the bile of mammals. They play many
important biological functions, as in the metabolism of lipids for
their ability to form mixed micelles, which interact with lipid
bilayers of biological membranes and mediate transport of
lipophilic compounds through the intestinal membrane. [2]
We envisaged that, by combining the above described two
structural units into one single entity, we could obtain
a Metal-Salophen / Bile Acid conjugate possessing novel
properties in terms of anion binding and transport. 1H NMR and
UV-vis studies demonstrate that the Zn-chelate, 1, binds anions
in DMSO, but the addition of 10% water severely hampers the
binding. More importantly, the bile acid moieties in 1 render it
capable of being incorporated into CTAB micelles. Using CTABr
micelles as carriers for anion receptors is indeed a convenient way
to test their anion binding properties in water. [3] Under such
conditions, 1 is able to bind phosphate with a relatively high
affinity (K ca. 500 M-1 ). TEM microscopy and Dynamic Light
Scattering studies highlight the influence that 1 and anions have
on the size and shape of the CTABr micelles. These are important
aspects that must be considered to fully evaluate the binding
properties of the Zn-chelate / CTABr supramolecular system
which resulted in being an efficient anion binder in the highly
competitive water medium.
references:
1. Dalla Cort A., Bernardin De P., Forte G., Mihan Yefteh F.,
Chem. Soc. Rev. 2010, 39, 3863.
2. Virtanen E., Kolehmainen E., Eur. J. Org. Chem. 2004, 16,
3385.
3. Cametti M., Dalla Cort A., Bartik K., ChemPhysChem
2008, 15, 2168.
Keywords: micelles; click chemistry; anions; UV/Vis
spectroscopy; Steroids;
AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc