Asymmetric oxidative dearomatization of arenes with biologically inspired oxidation catalysts
ENG- This thesis investigates the development and application of bioinspired iron and manganese complexes as catalysts for the dearomative oxidation of non-activated arenes, focusing on epoxidation and syn-dihydroxylation reactions. These transformations are particularly difficult because of the inh...
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| Tipo de recurso: | tesis doctoral |
| Estado: | Versión publicada |
| Fecha de publicación: | 2025 |
| País: | España |
| Institución: | CBUC, CESCA |
| Repositorio: | TDR. Tesis Doctorales en Red |
| OAI Identifier: | oai:www.tdx.cat:10803/694497 |
| Acceso en línea: | http://hdl.handle.net/10803/694497 |
| Access Level: | acceso embargado |
| Palabra clave: | Catàlisi asimètrica Catálisis asimétrica Asymmetric catalysis Peròxid d'hidrogen Peróxido de hidrógeno Hydrogen peroxide Sin-dihidroxilació Sin-dihidroxilación Syn-dihydroxilation Epoxidació Epoxidación Epoxidation Catalitzador de manganès Catalizador de manganeso Manganese catalyst Catalitzador de ferro Catalizador de hierro Iron catalyst Catálisis oxidativa Oxidative catalysis 54 |
| Sumario: | ENG- This thesis investigates the development and application of bioinspired iron and manganese complexes as catalysts for the dearomative oxidation of non-activated arenes, focusing on epoxidation and syn-dihydroxylation reactions. These transformations are particularly difficult because of the inherent stability of aromatic systems. This steadiness likely explains the limited number of known examples. The comparison and contrast with the reactivity of alkenes is quite illustrative since these readily undergo a variety of oxidation reactions with a number of reactants. While being challenging, arene dearomatization reactions are very appealing because they transform the flat structure of the arene in functionalized and stereochemically rich 3D cyclohexyl moieties. These structures are of immediate interest as building blocks for medicinal chemistry and synthesis of natural products. The targeted reactions in this thesis will mirror the extraordinary reactivity of certain iron dependent enzymes. In particular, the known arene epoxidation activity displayed by heme P450 enzymes and the arene syn-dihydroxylating activity of several Rieske oxygenases. The reactivity exhibited by these enzymes strongly support the hypothesis that high valent metal oxo compounds have the capability to overcome the poor reactive character of arenes under mild conditions. Therefore, we reasoned that biomimetic catalysts based in small molecule coordination complexes that can generate high valent metal-oxo species may reproduce this activity and become valuable catalysts. With these considerations in mind small molecule iron and manganese catalysts that can sustain high oxidation states have been explored as dearomative oxidation catalysts. By performing these transformations in both non-enantioselective and enantioselective manners, we aim to expand the synthetic toolkit available for the development of complex molecules starting from simple aromatic precursors. In conclusion, this work substantially contributes to the field of arene oxidation, introducing new catalytic systems capable of mimicking enzymatic processes and expands the possibilities for the obtention of complex molecules starting just from simple aromatic precursors |
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