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NEW POLIARENES. TOWARDS THE SYNTHESIS OF NON-PLANAR AROMATIC HYDROCARBONSAuthor: GONZÁLEZ CANTALAPIEDRA ESTHER. Year: 2004. University: AUTÓNOMA DE MADRID. Place of defense: FACULTAD DE CIENCIAS. Place of preparation: FACULTAD DE CIENCIAS. Summary: Summaries of derivatives truxeno for obtaining new planes not polycyclic aromatic hydrocarbons by reaction arilación intramolecular catalysed by Pd. APPLICATIONS REACTIONS CICLOADICIÓN 2 +2 +2 OF ARINOS CATALYZED BY PALLADIUM. I SUMMARIES ENANTIOSELECTIVA OF PENTAHELICENOS. II. SUMMARIES OF POLYCYCLIC SYSTEMS RELATED N. FENILENOS.Author: CAEIRO RODRÍGUEZ JORGE. Year: 2005. University: SANTIAGO DE COMPOSTELA. Place of defense: FACULTAD DE QUÍMICA. Place of preparation: FACULTAD DE QUÍMICA.
Summary: This dissertation focuses on the study of new applications lasa reactions cicloadicción (2 +2 +2) of arinos catalyzed by palladium complexes. Specifically, the first part of the thesis has shown that it is possible the synthesis enantioselectiva of (5) helicenos funcionalizados through reaction cocicloadición (2 +2 +2) of arinos with alquinos catalyzed by palladium complexes containing fosfinas saw toothed chiral. Although the study results can not be regarded as satisfactory from the point of view sinético, if they are significant because it is the first evidence of asymmetric catalysis inthe involved arinos, and because, in our view, constitute the second known instance of catalysis enantioselectiva applied to building skeletons helical and the third in a reaction cicloadición (2 +2 +2). In the second part, have addressed the synthesis of polycyclic new systems with symmetry D3 in the three units (N) phenylene are condensed to a ring bencénico central topology that these compounds may provide some physical and chemical properties peculíares. Of the molecules under study, has been the synthesis of a new system policíclico, a result of ciclotrimerización catalyzed by palladium's arino derivative (4) phenylene trianuglar. EMPLOYMENT ALFA'-HIDROXICETONAS DERIVED FROM CAMPHOR IN OBTAINING ESTEREOCONTROLADA FRAGMENTS GAMMA-AMINO-BETA-HIDROXIÁCIDO AND ESTEREOCENTROS QUATERNARY. APPLICATION IN THE SYNTHESIS OF DOLASTATINA 10 AND HAPALOSINAAuthor: BAÑUELOS VILLAVERDE PATRICIA. Year: 2005. University: PÚBLICA DE NAVARRA. Place of defense: DEPARTAMENTO DE QUÍMICA APLICADA. Place of preparation: DEPARTAMENTO DE QUÍMICA APLICADA. Summary: In this Doctoral Thesis explores the applicability of two inductors derived from chiral R (+) -alcanfor in reactions addition aldólica with alfa-aminoaldehídos and adding Michael with beta-cetoésteres alfa-sustituidos respectively. As a result of these studies have been able to establish the following conclusions: * The use of enolato lytic a metilcetona derived from camphor in reactions addition aldólica with alfa-aminoaldehídos allows access, with perfect diastereocontrol, fragments gama-amino beta - hidroxiácido. This methodology has enabled us to synthesize the fragment peptídico N-Cbz-Val-Val-Dil derived fragments Dov-Val-Dil present at the Dolastatina 10 and Hapalosina, natural products of biological interest. * On the other hand, describes a new synthesis of Hapalosina using agents macrociclación novel, obtaining yields higher than those obtained in other synthesis detailed in the literature. * Finally, it describes for the first time a general procedure pair's reaction adding between beta-cetoésteres alfa-sustituidos and Michael compounds carbonílicos alpha beta-insaturados derived from camphor, which leads to the generation of compounds with quaternary centers in a highly diastereoselectiva. Moreover, the procedure described permits, after oxidation of adducts of addition, the acquisition of carboxylic acids with high enantiomeric purity. SEARCH FOR NEW PLAYERS QUIMIOTERAPICOS: ANALOGS FENSTATINAS AND TAXOIDESAuthor: ALVAREZ SANJUAN CONCEPCION. Year: 2005. University: SALAMANCA. Place of defense: EDIFICIO HISTORICO. Place of preparation: FACULTAD DE FARMACIA. Summary: The interests of our working group in recent years has focused on the search for new compounds with cytotoxic activity, acting by inhibiting tubulin polymerization by binding to the site of colchicine. Moreover, it has recently launched a new line of investigation led to the search for compounds that join the site taxoides, with the aim of obtaining similar to a simpler structure. In work carried out in the dissertation have addressed both lines. Of the wide variety of compounds that bind to the site of colchicine, for this work were selected as a model the combretastatinas and fenstatinas, the latter compounds rare in literature and very interesting. We have synthesized a large number of fenstatinas, new derivatives modified on the bridge and the two aromatic rings and there have been all these compounds testing inhibition of tubulin polymerization and cytotoxicity, obtaining results very interesting. The simplified analogs of taxol have been designed on a basic structure of diciclopentadieno. This is a rigid system, which allows the incorporation of various substituents in the areas that coincide with the space occupied by the substituents present in the molecule of paclitaxel, as has been shown through studies of molecular modeling. REACTIONS DESHIDRO DIELS-ALDER SYSTEMS ARIL- AND HETEROARILACETILÉNICOSAuthor: MARTÍNEZ ESPERÓN MARÍA FERNANDA. Year: 2005. University: SANTIAGO DE COMPOSTELA. Place of defense: FACULTAD DE FARMACIA. Place of preparation: FACULTAD DE QUÍMICA.
Summary: It conducted a study of the reaction deshidro Diels-Alder in various systems. In the case of ciclación of arilpropinonas found the formation of the two products benzo [b] fluorenonas (product line) and benzo [c] fluorenonas (transposed products, formed by transposition of aleno cyclical initially formed), which depends on the proportion nature's replacement of arilo reagent. It was observed that there is a relationship between wealth electronics group arilo that reacts and transliteration of aleno cyclical. The greater wealth electronic arilo, which depends on the type of replacement who possesses, the higher the proportion of benzo [c] fluorenonas, caused by the transposition alénica, compared with the benzo [b] fluorenonas expected, and say, transposition. The substituents at position goal, whatever their nature electronic favors obtaining benzo [b] fluorenonas. The substitution in the ortho position and the appropriate choice of solvent offers a choice between obtaining benzo [b] - or benzo [c] fluorenonas. The reaction was also applied to inmaidas allowing the collection of benzo [b] carbazoles composed of great importance due to their varied biological activities and its usefulness for the synthesis of new organic materials. We continued the study of ciclaciones doubles type deshidro Diels-Alder that allow access to systems biarilicos heterocyclic present in the structure wide variety of chiral catalysts. For the studies carried out in this thesis is based on economic and commercial substances used a method ciclación heat which avoids the use of metal catalysts. RELATIVE STABILITY OF COMPOUNDS ORGANOLÍTICOS POLIFUNCIONALIZADOS AND APPLICATIONS OF SYNTHETIC REGROUPING ESTANNA-BROOKAuthor: MONJE FERNÁNDEZ PABLO. Year: 2006. University: SANTIAGO DE COMPOSTELA. Place of defense: FACULTAD DE QUÍMICA. Place of preparation: FACULTAD DE QUÍMICA.
Summary: It has devoted a part of the doctoral thesis on the development of a methodology based on the balance of transmetalación M-Li (M = Sn, Pb), which helps determine the relative stability of compounds alpha-oxiorganoliticos that presentna different groups of protectors on the alpha oxygen atom in the center carbaniónico and different sustituyeres on it, doing further studies of the state of aggregation of anions by NMR in solution at low temperatures. In the second part of the report describes the discovery of a novel reaction desearomatización bis-alquilación of diesters aromatic and heteroaromático promoted by Me3SnLi, which have gained alquilaciones and ciclaciones in one step and so regioselectiva, resulting in compounds bicíclicos useful synthetic.
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