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Synthesis and Use of Transition Metal Complexes with Helical Ligands
Žádný, Jaroslav ; Vojtíšek, Pavel (advisor) ; Kotora, Martin (referee) ; Růžička, Aleš (referee)
The Thesis describes our successful endeavour to develop asymmetric synthesis of functionalized 2H-pyran or 2,7-dihydrooxepine helicene-like compounds in an optically pure form. These helicene surrogates were fully characterized and their use in enantioselective catalysis as chiral ligands, organocatalysts or chiral modifiers was explored. A general method for the preparation of optically pure [5]- and [6]heterohelicenes by asymmetric synthesis is based on highly diastereoselective [2+2+2] cycloisomerization of centrally chiral triynes mediated/catalyzed by transition metal complexes. Stereochemical outcome of the cyclization process is controlled by 1,3-allylic-type strain. This new methodology is highly versatile providing an easy access to chiral ligands, organocatalysts or modifiers in a nonracemic form. Optically pure 2,7-dihydrooxepine [5]helicene-like phosphite ligands were explored in enantioselective allylic amination under catalysis by iridium(I) complexes to reach up to 82% ee. An organocatalysts represented by the optically pure 2H-pyran [5]helicene-like DMAP analogue was synthesized and applied to kinetic resolution of racemic sulfoximines. Finally, various functionalized derivatives of helicenes and helicene-like compounds (azahelicenes, DMAP analogues, (thio)urea derivatives) were...
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Complexation Properties of Aza[n]phenacene Ligands.
Váňa, Lubomír ; Žádný, Jaroslav ; Storch, Jan ; Církva, Vladimír
This work is aimed at the synthesis of new aza[n]phenacenes 2 (n = 4 or 5, Ar = phenyl or 2-pyridyl), where [njphenacenes 1 with ö-lactam ring are used as starting material. The resulting compounds are subsequenttly investigated in terms of their complexation properties with transition metals (Cu, Ni, Co, Pt, Ir) due to their potential application as photoluminescent complexes.
Fulltext: content.csg -  DOC
Plný tet: 00206B6C274C191114122808 - DOC
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Modification of Metal Surfaces by Optically Active [7]Helicene Derivatives for Molecular Sensing.
Walaská, Hana ; Kalachyova, Y. ; Elashnikov, R. ; Storch, Jan ; Žádný, Jaroslav ; Lyutakov, O.
New derivatives of 9-(pyridylethynyl)[7]helicenes were firstly prepared and fully characterized in this study. Consequently, they were successfully separated to their (P)- and (M)-enantiomers using a preparative HPLC with chiral stationary phase. These optical antipodes were advantageously used for modification of silver plasmon active nanogratings suitable for a SERS-based detection of (bio)molecules. Properties of such nanostructures were studied using different spectro- and microscopic techniques. As proved by UV-Vis spectrometry, a change of plasmon resonance wavelength position and intensity was observed and indicated the appearance of chiral surface plasmon polarization.
Fulltext: content.csg -  PDF
Plný tet: SKMBT_C22018110615053 - PDF
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Synthesis of Steroid Derivatives for In Vitro Diagnostics.
Kos, Martin ; Váňa, Lubomír ; Žádný, Jaroslav ; Storch, Jan
This work is focused on the synthesis of novel steroidal androgen derivatives consisting of a steroidal skeleton, a spacer and imidazole ring or a primary amine functional group. The starting material for the synthesis is represented by commercial available hydroxy-androgens, which are further modified. First, the hydroxyl group is attached to the spacer and then connected to the desired imidazole or the protected primary amine. The above described derivatives will be utilized for development of analytical kits for a determination of the free steroid hormone.
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