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Charles University, Faculty of Pharmacy in Hradec Králové Department Department of Organic and Bioorganic Chemistry Candidate Mgr. Petr Matouš Supervisor prof. RNDr. Milan Pour, Ph.D. Titel of Doctoral Thesis Gold-Catalyzed Cyclizations of 1,5-Enynes This Ph.D. thesis deals with the development of gold(I)-catalyzed cyclizations of propargylamino acrylates (3-aza-1,5-enynes) in the presence of an external nucleophile. A library of tetrahydropyridines with an unusual hemiaminal ether functional group was thus prepared via the cyclization of a series of substituted enynes. The influence of the protective group as well as the substitution on the chemoselectivity of the reaction was demonstrated. The tetrahydropyridines were further utilized as precursors for the preparation of pharmaceutically important nitrogen heterocycles. The reduction of selected compounds furnished substituted piperidines, while Diels-Alder cycloaddition of alkenylated tetrahydropyridines gave rise to isoquinoline derivatives. Additional ortho-fused heterocycles (furopyridine, pyrrolopyridine and chromenopyridine) were prepared by the intramolecular version of the cyclizations of enynes with pending internal nucleophiles.

This bachelor thesis is focused on using levoglucosenone in the synthesis of the naphthoquinone containing compounds. Levoglucosenone is a versatile and easily available substance which can be prepared by pyrolysis of renewable cellulose-containing materials. The synthesis of the target compound begins with the preparation of the substrate for the tandem reaction (propargyl ether) in three steps. The following key steps of the synthesis include palladium-catalyzed tandem cyclization/Suzuki cross coupling and subsequent Heck reaction. Oxidation of the prepared methoxy-substituted naphthalene yields the o-naphthoquinone, which has a similar structure as some naturally occurring substances with naphthoquinone skeleton, e.g. mansonone D and populene C. Key words: Synthesis, naphthalenes, naphthoquinones, levoglucosenone, catalysis, polycyclic compounds

This bachelor's thesis focuses on the synthesis of a polycarbocyclic compound with naphthalene core and the following oxidation to the corresponding ortho-naphthoquinone. The naphthalene and naphthoquinone skeleton can be found in many natural products with interesting biological properties. This thesis extends the scope of a method developed by our group for the synthesis of naturally occurring ortho-naphthoquinones. The key step of the synthesis was to form an aromatic ring using the Heck reaction. Keywords: synthesis, polycyclic compounds, naphthalenes, catalysis, Heck reaction

Bolm`s ligand belongs to the group of 2,2'-bipyridines, which represents a class of C2 symmetric ligands. These ligands form complexes with Lewis acids, which could be used in asymmetric catalysis, for example in the ring-opening of epoxides. Bolm`s ligand analogue was prepared and the enantioselectivity of the ring-opening reaction of cis-stilben oxide with aniline and variety of substituted benzyl alcohols catalyzed by scandium(III) triflate was studied as a part of this bachelor thesis. The enantioselectivity of the reaction using Bolm's ligand analogue was compared to that of Bolm`s ligand. Key words: synthesis, catalysis, bipyridines

In this diploma Thesis, a method for the preparation of polycarbocyclic compounds containing all-carbon quaternary centers embedded in triquinane skeleton was prepared. The key reaction sequence leading towards the preparation of these carbocycles was Pd-catalyzed tandem cyclization/Suzuki cross-coupling reaction followed by halocarbocyclization. In the first part of synthetic project, a model oxygen-containing polycyclic derivative was prepared. In the second part, 3 novel polycarbocyclic compounds containing all-carbon quaternary centers were successfully prepared. Synthetic procedure for the starting material required for the key reaction sequence was developed. This approach represents another pathway for the synthesis of polycarbocyclic natural products. Keywords: synthesis, polycyclic compounds, quaternary centers, catalysis