Aplicaciones derivadas de la fotoquímica de O-aciloximas
This Thesis deals with the applications of acyloximes. The irradiation of these compounds generates iminyl radicals which can lead to nitrogen containing heterocycles by ring closure. Aims are described (Chapter 3) after an introduction (Chapter 1) and a background (Chapter 2). In this chapter, the...
Guardado en:
| Autor principal: | |
|---|---|
| Otros Autores: | |
| Formato: | text (thesis) |
| Lenguaje: | spa |
| Publicado: |
Universidad de La Rioja (España)
2012
|
| Acceso en línea: | https://dialnet.unirioja.es/servlet/oaites?codigo=40347 |
| Etiquetas: |
Agregar Etiqueta
Sin Etiquetas, Sea el primero en etiquetar este registro!
|
| id |
oai-TES0000005676 |
|---|---|
| record_format |
dspace |
| institution |
DialNet |
| collection |
DialNet |
| language |
spa |
| description |
This Thesis deals with the applications of acyloximes. The irradiation of these
compounds generates iminyl radicals which can lead to nitrogen containing
heterocycles by ring closure.
Aims are described (Chapter 3) after an introduction (Chapter 1) and a
background (Chapter 2). In this chapter, the photochemical reactivity of acyloximes
and the reaction mechanism studies throughout experimental and computational
techniques are summarized.
In Chapter 4, it is explained how the acyloximes are irradiated in the presence of
alkynyl Fischer carbene complexes, which constitutes the first example of a
photochemically driven reaction of this kind. When the radical participates in a 1,4-
addition to alkynylcarbene complexes 5-aza-1-metalla-1,3,5-hexatriene where
obtained, while the 1,2 addition led to azepines.
In Chapter 5, the synthesis of more complex acyloximes to give new nitrogen
containing heterocyclic compounds by the photochemically generated iminyl
radicals is described. This strategy also has been used to obtain natural products,
such as trisphaeridine and the precursor of some alkaloids, such as vasconine,
assoanine, oxoassoanine and pratrosine.
In Chapter 6, the first trisphaeridine derivatives substituted on both the 7- and
10- positions of phenanthridine skeleton are described. Moreover, the effect of the
substituents has been elucidated by studying the electrochemical and photophysical
properties of the new compounds. These studies have been supported by DFT and
TDDFT calculations. Finally, it was found that these new trisphaeridine derivatives
are fluorescent. Therefore, they are capable of detecting protons and metal ions
depending on the substituent because of the fact that changes in their fluorescence
spectra are observed. In conclusion, we have obtained new compounds that can be
used as fluorescence sensors. |
| author2 |
Campos García, Pedro José (Universidad de La Rioja) |
| author_facet |
Campos García, Pedro José (Universidad de La Rioja) Caballero Millán, Alegría |
| format |
text (thesis) |
| author |
Caballero Millán, Alegría |
| spellingShingle |
Caballero Millán, Alegría Aplicaciones derivadas de la fotoquímica de O-aciloximas |
| author_sort |
Caballero Millán, Alegría |
| title |
Aplicaciones derivadas de la fotoquímica de O-aciloximas |
| title_short |
Aplicaciones derivadas de la fotoquímica de O-aciloximas |
| title_full |
Aplicaciones derivadas de la fotoquímica de O-aciloximas |
| title_fullStr |
Aplicaciones derivadas de la fotoquímica de O-aciloximas |
| title_full_unstemmed |
Aplicaciones derivadas de la fotoquímica de O-aciloximas |
| title_sort |
aplicaciones derivadas de la fotoquímica de o-aciloximas |
| publisher |
Universidad de La Rioja (España) |
| publishDate |
2012 |
| url |
https://dialnet.unirioja.es/servlet/oaites?codigo=40347 |
| work_keys_str_mv |
AT caballeromillanalegria aplicacionesderivadasdelafotoquimicadeoaciloximas |
| _version_ |
1718346609668915200 |
| spelling |
oai-TES00000056762019-06-21Aplicaciones derivadas de la fotoquímica de O-aciloximasCaballero Millán, AlegríaThis Thesis deals with the applications of acyloximes. The irradiation of these compounds generates iminyl radicals which can lead to nitrogen containing heterocycles by ring closure. Aims are described (Chapter 3) after an introduction (Chapter 1) and a background (Chapter 2). In this chapter, the photochemical reactivity of acyloximes and the reaction mechanism studies throughout experimental and computational techniques are summarized. In Chapter 4, it is explained how the acyloximes are irradiated in the presence of alkynyl Fischer carbene complexes, which constitutes the first example of a photochemically driven reaction of this kind. When the radical participates in a 1,4- addition to alkynylcarbene complexes 5-aza-1-metalla-1,3,5-hexatriene where obtained, while the 1,2 addition led to azepines. In Chapter 5, the synthesis of more complex acyloximes to give new nitrogen containing heterocyclic compounds by the photochemically generated iminyl radicals is described. This strategy also has been used to obtain natural products, such as trisphaeridine and the precursor of some alkaloids, such as vasconine, assoanine, oxoassoanine and pratrosine. In Chapter 6, the first trisphaeridine derivatives substituted on both the 7- and 10- positions of phenanthridine skeleton are described. Moreover, the effect of the substituents has been elucidated by studying the electrochemical and photophysical properties of the new compounds. These studies have been supported by DFT and TDDFT calculations. Finally, it was found that these new trisphaeridine derivatives are fluorescent. Therefore, they are capable of detecting protons and metal ions depending on the substituent because of the fact that changes in their fluorescence spectra are observed. In conclusion, we have obtained new compounds that can be used as fluorescence sensors.En esta Memoria se exponen diversas aplicaciones de las O-aciloximas, compuestos que al ser irradiados fotoquímicamente, generan un radical iminilo que es capaz de ciclar para dar lugar a heterociclos nitrogenados. Los objetivos de este Trabajo se detallan en el Capítulo 3 después de una pequeña introducción y de la exposición de los Antecedentes (Capítulo 2). En este último, se resume la reactividad fotoquímica de las O-aciloximas y su mecanismo de fotorreactividad por medio de técnicas experimentales y computacionales. En el Capítulo 4, las O-aciloximas son irradiadas en presencia de carbenos de Fischer, lo que constituye el primer ejemplo descrito de este tipo de reacciones. Se ha demostrado que el radical iminilo generado fotoquímicamente, es capaz de adicionarse a alquinil carbenos de Fischer dando lugar a 5-aza-1-metala-1,3,5- hexatrienos mediante un mecanismo de adición 1,4; y a azepinas, si la adición se efectúa de forma 1,2. En el Capítulo 5, se han sintetizado O-aciloximas más complejas para obtener nuevos heterociclos nitrogenados mediante la ciclación fotoquímica del radical iminilo. Esta metodología ha sido utilizada para sintetizar productos naturales como la trisferidina y el precursor de alcaloides como la vasconina, pratosina, assoanina y oxoassoanina. En el Capítulo 6, se sintetizan por primera vez compuestos derivados de trisferidina al incorporar sustituyentes en las posiciones 7 y 10 del anillo de fenantridina. Se han estudiado las propiedades electroquímicas y fotofísicas de estos compuestos y se han completado con cálculos teóricos DFT y TDDFT. Además, hemos comprobado que este tipo de derivados son fluorescentes y que son capaces de detectar protones e iones metálicos al observarse cambios en los espectros de fluorescencia. Por lo tanto, se han sintetizado nuevos compuestos que pueden utilizarse como sensores fluorescentes.Universidad de La Rioja (España)Campos García, Pedro José (Universidad de La Rioja)Rodríguez Barranco, Miguel Angel (Universidad de La Rioja)2012text (thesis)application/pdfhttps://dialnet.unirioja.es/servlet/oaites?codigo=40347spaLICENCIA DE USO: Los documentos a texto completo incluidos en Dialnet son de acceso libre y propiedad de sus autores y/o editores. Por tanto, cualquier acto de reproducción, distribución, comunicación pública y/o transformación total o parcial requiere el consentimiento expreso y escrito de aquéllos. Cualquier enlace al texto completo de estos documentos deberá hacerse a través de la URL oficial de éstos en Dialnet. Más información: https://dialnet.unirioja.es/info/derechosOAI | INTELLECTUAL PROPERTY RIGHTS STATEMENT: Full text documents hosted by Dialnet are protected by copyright and/or related rights. This digital object is accessible without charge, but its use is subject to the licensing conditions set by its authors or editors. Unless expressly stated otherwise in the licensing conditions, you are free to linking, browsing, printing and making a copy for your own personal purposes. All other acts of reproduction and communication to the public are subject to the licensing conditions expressed by editors and authors and require consent from them. Any link to this document should be made using its official URL in Dialnet. More info: https://dialnet.unirioja.es/info/derechosOAI |