Theoretical investigation of microporous materials for adsorption and catalysis Microporous materials are defined by a presence of pores with diameter smaller than 2 nm. They comprise a large variety of materials from amorphous materials to very well defined crystalline materials like zeolites or metal organic frameworks. Microporous materials are industrially very important group of materials used for adsorption, gas capture, molecular sieving, or heterogeneous catalysis. Zeolites are by far the most important group of microporous materials due to their use as catalysts for the petroleum cracking. One of the main limitations of the zeolite use in catalysis is their limited pore size. This obstacle can be solved by use of hierarchical zeolites with a secondary mesopore network which allows overcoming the diffusion problems. The aims of this study can be divided into two parts. In the first part, the structures of two-dimensional and hierarchical zeolites were investigated theoretically to identify the structure of new materials and to obtain reliable models to study the hierarchical zeolites. In the second part, the catalytic properties of several microporous materials were modelled to explain their experimental activity. The results of this thesis were used to identify the structure of a large...

E-492, actinofuranone A, and JBIR-108 are natural compounds isolated from actinobacteria Streptomyces genus and can lead to the development of new pharmaceuticals as they have some biological interesting activities. Although the synthesis of these actinofuranones has been already published, this work brings new methods for the preparation of their fragments. The key step of the synthesis is enantioselective crotylboration of an aldehyde catalyzed by a chiral Brønsted acid and by which two centres of chirality are introduced in one step. The other crucial steps of the synthesis are composed of Ru-catalyzed alkene-alkene cross-metathesis and Pd- catalyzed Suzuki cross-coupling. Keywords: natural compound, enantioselective syntheses, crotylation, catalysis, actinofuranone fragment

In this work, we report the study of the catalytic activity of newly prepared coordination compounds of nickel(II) (complexes were prepared by prof. Kyritsis, University of Athens). The activities in model reactions of Kumada and Suzuki coupling and polymerization of 2,5- dibromo-3-hexylthiophene were tested. For Kumada coupling, the activity is comparable with known complex [Ni(dppp)Cl2]. On the other hand, selected complexes exhibit only limited activity for Suzuki coupling. GRIM polymerization of 2,5-dibromo-3-hexylthiophene was successful. Properties of prepared polymers are comparable with polymers prepared via known route with [Ni(dppp)Cl2].

This work consists of four consecutive parts, each dealing with syntheses of structurally diverse compounds. The syntheses were based on the methods within the domain of transition-metal catalyzed and/or mediated reactions with particular emaphasis on the application of organozirconium chemistry. 1. A method for synthesis of tricyclic condensed hydrocarbons possessing 5(6)-7-6(aryl) framework was developed. It is based on reaction of bicyclic zirconacyclopentenes, prepared by oxidative dimerization of enynes on a low-valent zirconocene species (Negishi's reagent), with ortho-halobenzaldehydes in the presence of various additives. The presence of two different centers of reactivity - the sp2 C-Zr and sp3 C-Zr bond - allowed sequential functionalization of each bond. Thanks to its higher nucleophilicity, the sp3 C-Zr bond reacted preferentially with the carbonyl carbon of the aldehyde yielding an oxazirconacycloheptene. The subsequent transmetallation of the remaining sp2 C-Zr bond with CuCl in the presence of other additives (catalysts) enabled an intramolecular cross-coupling reaction with the aryl halide moiety furnishing the desired tricyclic products in reasonable yields. The scope of the reaction with respect to differently functionalized reactants was assessed, as well as its mechanistic...

This work is divided into two parts that are focused on the synthesis and assessment of photophysical properties of two structurally related compounds: (i) 9,9'-spirobifluorenes (SBFs) and (ii) dispiroindeno[2,1-c]fluorenes (DS-IFs). (i) In the first part, a five-step synthetic approach to SBFs was developed and as the crucial step was used an intermolecular [2+2+2] cyclotrimerization of symmetrically or unsymmetrically substituted diynols with alkynes catalyzed by Rh-complexes. Catalyst screening showed that Wilkinson's catalyst (RhCl(PPh3)3) had the highest efficiency in yielding 1,2,3,4-substituted fluorenols - the key intermediates. The fluorenols were then converted into SBFs bearing various electron-donating and -withdrawing groups, aromatic substituents, and -extended aromatic hydrocarbon moieties (PAHs). Altogether 19 different SBFs were prepared and their photophysical properties screened. The fluorescent emission maxima em were in the range of 315-389 nm with excellent quantum yields s (up to 1.00). As far as the substituent effect is concerned the presence of electron-withdrawing substituents on the SBF scaffold results in the red-shift of the emission maxima. (ii) In the second part, a similar synthetic strategy was applied for synthesis DS-IFs. In this instance was utilized again the...

2,2'-Bipyridines and their appropriate N,N'-dioxides form a significant class of heteroaromatic compounds, which has found application in various fields of chemistry and predominantly in asymmetric catalysis. One of the most powerful methods for their synthesis is cocyclotrimerization of alkynes with nitriles. A new variant of cyclotrimerization reaction - cocyclotrimerization of halodiynes with nitriles, which results in the formation of 2- and 3-halopyridines, has been developed. The reaction was studied on a wide range of substrates providing the pyridine products in good isolated yields. Formation of an unexpected product of halogen exchange reaction was observed during the course of the study and its origin was elucidated by experimental studies. The prepared 2-halopyridines were used as starting materials for syntheses of new chiral 2,2'-bipyridine ligands. The crucial step of their synthesis turned out to be the reductive dimerization of 2-halopyridines to the corresponding 2,2'-bipyridines. Application of the formed bipyridine ligands was then tested in various metal-catalyzed asymmetric reactions, namely Mukaiyama aldol reaction, hydroxymethylation, conjugate addition, C-H activation of indole and desymmetrization of meso-epoxides, in which one of the bipyridine ligands showed...

The "Ferrocene phosphinoguanidine donors" project presented in this Thesis targeted on the synthesis, coordination chemistry and catalytic applications of a rather uncommon class of compounds combining phosphine and guanidine functional groups in their molecules. Two series of such compounds based on ferrocene backbone (henceforth fc = ferrocen-1,1΄-diyl) were studied. Firstly, a reliable synthetic route towards polar phosphinoguanidinium chlorides [R2PfcCH2NHC(NH2)2]Cl, where R = iso-propyl, cyclohexyl, phenyl and 2-furyl, was developed and these ligands were tested as supporting ligands in palladium-catalysed Suzuki-Miyaura-type reactions in biphasic aqueous mixtures and in rhodium-catalysed hydroformylation of 1-hexene. Deduced from the results, the hydrophilic guanidinium tag had a beneficial effect on the catalytic activity and, particularly, the electron-rich phosphines from this series could serve as a useful alternative to commonly used ligands for catalytic applications in polar or aqueous reaction media. Phosphinonitriles R2PfcCN obtained as intermediates during the synthesis of the abovementioned ligands were additionally used for the preparation of the dimeric complexes [Au2(µ-R2PfcCN)2][SbF6]2, in which the gold(I) centre was stabilised by nitrile coordination. These complexes proved...

1 Abstract Due to the presence of small structural units (e.g., D4R, D3R), the frameworks of germanosilicate zeolites are generally characterized by high pore volumes and multidimensional/extra-large pore systems, making them especially suitable in processing bulky molecules (in particular, involved in biomass-derived compounds valorization). However, weak acidity, low hydrothermal stability and high cost of Ge significantly limit the practical use of Ge-containing zeolites. This thesis is aimed at design of sustainable germanosilicate zeolite-based catalysts of modifiable chemical composition and tunable porosity for relevant acid-catalyzed reactions, such as ketalization of polyols, epoxidation of olefins, Baeyer-Villiger oxidation of cyclic ketones and Meerwein-Ponndorf-Verley reduction of aldehydes. Germanosilicate zeolites of different structures, including medium-pore ITH, large pore IWW, extra-large pore UTL and *CTH, were thoroughly characterized using a combination of techniques (i.e., XRD, physisorption, electron microscopy, chemical analysis, among others) and subjected to different post-synthesis modifications to address synthesis-structure-activity relationships in the designed germanosilicate-zeolite based catalysts. In ketalization of glycerol to solketal, weak acid centers of IWW and UTL...

This diploma thesis is focused on the combination of enantioselective organocatalysis and transition metal catalysis. In the experimental part of the work, the optimization of reaction conditions with respect to the reaction yields, enantioselectivity and diastereoselectivity was solved. The applicability of the reaction was verified on various substrates. The second part of the work is focused on the study of the mechanism of the reaction using the methods of quantum chemistry. The kinetics of the reaction were monitored by NMR spectroscopy and the mechanism of the reaction was investigated by quantum chemistry methods. Keywords: aminocatalysis, palladium, synergistic catalysis, reaction mechanism, DFT

6 Abstract The first part of this Thesis describes the preparation of a novel phosphanyl-ferrocene amine, Ph2PfcCH2NH2 (1; fc = 1,1'-ferrocendiyl) in two steps from the known aldehyde Ph2PfcCHO. An oxime Ph2PfcCH=NHOH was prepared firstly by a condensation reaction, and subsequently treated with Li[AlH4] to give the desired amine. The amine was converted into its more stable hydrochloride salt, Ph2PfcCH2NH3Cl. Derivatization of amine 1 was examined through the preparation of a series of phosphanyl-urea ligands Ph2PfcCH2NHC(E)NR1 R2 . Some of these compounds were also prepared via an alternative method employing reductive amination reaction. These donors and their Pd(II) complexes were evaluated in Pd-catalyzed reaction of arylbromides with K4[Fe(CN)6] in order to prepare corresponding benzonitrile derivatives using aqueous reaction solvents. The reaction proceeds with excellent yields and purity when 1 mol.% of Pd- catalyst is used (at 100 řC for 3 hours), especially for electron-rich bromobenzenes. Substrates with electron-withdrawing substituents react significantly slower and corresponding hydrolytic products (benzamides) are isolated. The coordination properties of phosphanyl-amine 1 were examined towards Cu(I) ions. Thus, reaction of 1 with [Cu(MeCN)4][BF4] provided bis-chelate complex [Cu(1- κ2...