Nuevas estrategias sintéticas regio-y estereocontroladas de reagrupamiento y funcionalización basadas en alenos
Allenes have been considered very unstable compounds. This has caused a lack of knowledge in the scientific community of their chemical and synthetic applications for many years. However, in the last decades these molecules have experienced great growth in the field of organic synthesis due to their...
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| Tipo de recurso: | tesis doctoral |
| Fecha de publicación: | 2024 |
| País: | España |
| Institución: | Universidad Complutense de Madrid (UCM) |
| Repositorio: | Docta Complutense |
| Idioma: | español |
| OAI Identifier: | oai:docta.ucm.es:20.500.14352/103365 |
| Acceso en línea: | https://hdl.handle.net/20.500.14352/103365 |
| Access Level: | acceso abierto |
| Palabra clave: | 547.91(043.2) Alenos Química orgánica (Química) 2306 Química Orgánica |
| Sumario: | Allenes have been considered very unstable compounds. This has caused a lack of knowledge in the scientific community of their chemical and synthetic applications for many years. However, in the last decades these molecules have experienced great growth in the field of organic synthesis due to their interesting reactivity that allows a great variety of possible transformations.In this context, the general aim of this PhD Thesis is to develop new methodologies for the rearrangement and functionalization of allenes in order to obtain structurally novel compounds. To achieve this aim, this work has been divided into four chapters that are summarized below:1. A rhodium-catalyzed regioselective synthesis of 1,2-diketones containing a sulfonamide group and a 1,3-diene moiety in its structure has been accomplishedusing α-allenols and 4-substituted-N-sulfonyl-1,2,3-triazoles as starting materials through a Claisen type [3,3] sigmatropic rearrangement. 2. The controlled preparation of two types of α-seleno-α,β-unsaturated carbonyls, namely, α-selenoenals and α-selenoenones, has been accomplished directly from allenes through metal-free oxidative selenofunctionalization reactions. The decisive role of the organoselenium and 1-fluoropyridinium reagents has been disclosed. The divergent reactivity due to the presence or absence of an ethoxycarbonyl moiety at the allene end has also been studied. A tentative pathway implyng selective electrophilic addition of the selenium reagent to the allene moiety followed by adventitious water attack and concomitant oxidation has been proposed... |
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