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Catalytic testing of polar amidophosphines
Šrámková, Helena ; Štěpnička, Petr (advisor) ; Veselý, Jan (referee)
Catalytic testing of polar amidophosphines: abstract A series of new nine arylruthenium complexes [(aryl)RuCl2(L)] was studied in isomerisations of allylic alcohols to carbonyl compounds. The best reaction conditions were found. The best solvent and reaction temperature were chosen. The best amount of catalyst and the best base and its amount were chosen too. In these conditions, the catalysts were tested for four substituted allylic alcohols. It was proven that these catalysts isomerise readily simple allylic alcohols, but not substrates that is highly substituted.
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Asymmetric Tandem Lithium Amide Conjugate Addition/Radical Reactions and Their Application in the Total Synthesis of Natural Products
Hidasová, Denisa ; Jahn, Ullrich (advisor) ; Kočovský, Pavel (referee) ; Míšek, Jiří (referee)
This thesis deals with single-electron transfer (SET) radical processes mediated by ferrocenium hexafluorophosphate and TEMPO and their application in the total synthesis of natural products. Asymmetric aminooxygenation methodology for the synthesis of anti-β-amino-α-hydroxy acid derivatives has been developed by utilizing a highly diastereoselective aza-Michael addition of chiral lithium amides to various α,β-unsaturated esters or amides/SET oxidation/radical α-oxygenation. The potential of this methodology was demonstrated in short total syntheses of the anti-β-amino-α-hydroxy acid fragments of the macrocyclic (depsi)peptides perthamide C and largamide H, and (-)-cytoxazone, which is a selective modulator of TH2 cytokine secretion. The SET-catalyzed asymmetric tandem lithium amide conjugate addition/5-exo radical cyclization/oxygenation reactions were applied in the synthesis of highly substituted pyrrolidines, azabicyclo[n.3.0]alkanes and spiropyrrolidines. An enantioselective total synthesis of the pyrrolidine alkaloid (-)-α-kainic acid was accomplished by employing the SET-catalyzed 5-exo radical cyclization/oxygenation.
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Direct monitoring of metal-catalyzed reactions using electrospray ionization mass spectrometry
Tsybizova, Alexandra ; Roithová, Jana (advisor) ; Jahn, Ullrich (referee) ; Kvíčala, Jaroslav (referee)
The current dissertation thesis is focused on the investigation of metal-catalyzed reactions using electrospray ionization mass spectrometry as the primary research technique. However, other gas- phase methods such as tandem mass spectrometry, infrared multiphoton dissociation spectroscopy and quantum chemical calculations have also been involved to unravel and support the findings and proposals. As organometallic chemistry is a very broad and complicated topic, this thesis is only focused on a few projects. The fist of them is dedicated to copper acetate speciation in organic solvents, the second - to the mechanistic investigation of copper catalyzed aerobic cross coupling of thiol esters and arylboronic acids, the third studied coordination and bond activation of nickel(II) - phenylpyridine complexes and the last investigated carboxylate assisted C-H activation reactions.
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Catalytic testing of polar amidophosphines
Šrámková, Helena ; Štěpnička, Petr (advisor) ; Veselý, Jan (referee)
Catalytic testing of polar amidophosphines: abstract A series of new nine arylruthenium complexes [(aryl)RuCl2(L)] was studied in isomerisations of allylic alcohols to carbonyl compounds. The best reaction conditions were found. The best solvent and reaction temperature were chosen. The best amount of catalyst and the best base and its amount were chosen too. In these conditions, the catalysts were tested for four substituted allylic alcohols. It was proven that these catalysts isomerise readily simple allylic alcohols, but not substrates that is highly substituted.
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