ORGANIC CHEMISTRY

Author: AREVALO CABALLERO MARIA JOSE.
Year: 2002.
University: EXTREMADURA.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: In this Doctoral Thesis explores the synthesis of new systems 1,3-tiazolio-4-olato using tioureas and tioamidas derived from carbohydrate products departida, prepared from commercial products such as N-metil-D-glucamina and d - gluconolactona. Reactions cicloadición 1,3-dipolar of these systems with dipolarófilos acetilénicos, olefínicos and azodipolarófilos provide a simple method that allows us to synthesize a variety of N-and C-Nucleoside chain open. Specifically when new systems 1,3-tiazolio-4-olato synthesized react with acetilendicarboxilato Dimethyl get rings 2-piridona and thiophene. The reaction of these compounds cona zodicarboxilato Diethyl leads to triazine rings and thiazole ring. The new hetero mesoiónicos allow synthesize C-ni-cleósidos polycyclic and rings 1,2-dihidrotiofenos when reacting with dipolarófilos olefínicos as N-fenilmaleimida, 1,4-benzoquinona, 1,4-naftoquinona, vinyl methyl ketone, and methyl acrylate acrylonitrile.

Author: Fernández de las Nieves Ignacio.
Year: 2002.
University: ALMERÍA.
Place of defense: Universidad de Almeria.
Place of preparation: Universidadd de Almería.

Summary: This report reflects the work performed using fosfinamidas litiadas as intermediates in synthetic reactions ciclación anion intramolecular with desaromatización. Reactions desaromatización can transform N-benzyl and N-alildifenilfosfinamidas compounds readily available low-cost, but with high inertia chemical products with a degree of heterocyclic funcionalización variable. This thesis is composed of eight chapters, the first of which is a revision of the methods of desaromatización systems bencénicos and condensed ring: hydrogenation, Birch reduction, oxidation arenoles, and additions to aromatic systems activated. The latter option is especially significant because it allows the sequential addition of a nucleófilo and a electrófilo on the system aromatic. The second chapter describes the desaromatización for the first time, N-bencilfosfinamidas through reactions ciclación anion. The process passes with great estereoselectividad and high yields. On this basis, have been analyzed aspects such as the effect of solvent, cosolvente base organolítica, temperature and substituent on the nitrogen. The general reaction has been evident capturing the anion intermediates with a variety of agents protonantes, alkylating as well as aromatic and aliphatic aldehydes. The final structures were characterized by NMR, supported in the case by more representative measures X-ray Diffraction of monocristal, identifying in this way on the configuration of individual centers estereogénicos of the molecule. In addition, they were tested on measures of antitumor activity offer promising results. The application of the methodology developed in the previous chapter, the desaromatización of fosfinamidas enantioméricamente pure, has been evaluated in the third chapter. The results have shown that you can use ciclación anion with desaromatización to transform direct and estereoespecíficamente, a product line enantioméricamente pure single chiral center, in a tetrahidroazafosfol ciclohexadiénico also enantioméricamente pure, but with four or five centers estereogénicos, according to the . For example, the capture of the anions litiados with aldehydes, are generated two tetrahidroazafosfoles gamma-sustituidos enantioméricamente cigars, of the thirty-two possible stereoisomers. The anticancer activity tested in them does not differ significantly with respect to that obtained for derivatives racémicos generated in chapter two. The fourth chapter is a detailed analysis of the mechanism of the reaction desaromatización, evaluated from two standpoints primarily on dissolution studies through magnetic resonance multinuclear and gas phase through modeling the process using ab initio calculation methods and DFT. The NMR studies revealed the existence of a balance between two anions desaromatizados monomers which differ in configuration on phosphorus. These give rise to the end products when it adds a electrófilo the reaction. The monitoring of the reaction at temperatures close to freezing point of the solvent led to the characterization of different intermediate involved in the transformation: (1) a fosfinamida litiada in the ortho position of one of the groups P-fenilo characterized as a dímero, (2) an anion benzyl which is responsible for desaromatización by attack intramolecular one of the positions ortho a replacement phenyl coupled with phosphorus, (3) balance between anions desaromatizados monoméricos of phosphorus in the opposite configuration. The computational study shows that the ciclación anion from the center carbaniónico until aromatic poor electronically is Michael type, with the estereoselectividad of reaction heavily influenced by type estérico and mail. The extent of the reactions of desaromatización on substrates N-alílicos and difosfinamídicos has been explored in chapter five. The first one opens the possibility 8 to get abb er 1-óxido of tetrahidro-1-aza-2-fosfa-benzocicloheptenos systems consisting of the ring carbocíclico desaromatizado, merged a heterocyclic seven members. About the difosfinamidas has conducted a structural study by X-ray diffraction in which it has assessed the conformations taken in a free state and complexed. These variables have been applied to the design of difosfinamidas suitable for subsequent desaromatización. Chapter six is a compendium of transformations performed on primary products of desaromatización based on the breaking of the link fosfinamídico, creating acids and esters -aminofosfínicos. Similarly, we have developed hydrogenation reactions, epoxidación and isomerization on systems diénicos originals. About derivatives funcionalizados more representative, took place measures cytotoxicity, offering similar results to those from precursors unmodified. In the seventh chapter, have taken the initial steps to extend the methodology desaromatización of fosfinamidas other similar phosphorus, fosfacenos. In this first approach has been undertaken by the structural study of X-ray diffraction of the complex 91st with a fenolato very prevented estéricamente. Likewise, it has been established for the first time by X-ray diffraction, NMR and theoretical calculations, the structure of a N-metoxicarbonilfosfaceno similar metalado in carbon alpha regard to phosphorus. In solid state is as dímero, where lithium is coordinated at the center metalado and oxygen carbonílico, forming a metalaciclo six members. At dissolution establishing a balance monómero-dímero. While the study corroborate the theoretical allows greater stability in the cycle of six members with the one the coordination of lithium with nitrogen, in four stages. Finally, in the eighth chapter outlines the general procedures synthesis, as well as the complete characterization of all synthesized products.

Author: FONT GIMBERNAT DAVID.
Year: 2003.
University: GIRONA.
Place of defense: CIENCIAS.
Place of preparation: FACULTAT DE CIENCIES.

Summary: The present work has been desrrollado an effective methodology for obtaining various derivatives pririmidínicos with different degrees of molecular diversity. This methodology is based on the S-alquilación selective for 2-tiouraciles (2) bromide benzilo when working in solution or when Merrifield resin chemistry is on solid support. Then rent selectively elátomo oxygen of benzilsulfanilpirimidinonas (3) either by the reaction of Mitsunobu or using different rent of halides in the presence of a base. With 4-alcoxiporimidinas (4) are performed various chemical transformations, such additions Grignard (when R2 = CH2COph). Subsequently ocxida group sulfanilo to sulfone using m-CPBA and moves with the role sulfone deferent nucleotide.

Author: ARNÉS NOVAU XAVIER.
Year: 2003.
University: ROVIRA I VIRGILI.
Place of defense: QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: The 2-desoxi and 2,6-didesoxi glycosides are major structural units in a variety of natural products including anti-tumor drugs (anthracyclines as ciclamicina 0), antibiotics active against bacteria Gram-positivo (eritromicinas), which inhibit the antibiotics platelet aggregation (anguciclinas) and drugs used to treat heart failure (cardiac glycosides as digitoxina), antiparasitic agents (avermectinas), and so on. In this context, the objective of this work is to develop new methods of synthesis of 2-desoxi-oligosacáridos and stereoselective nucleoside from 2-desoxi-2-yodo-piranósidos and furanósidos. Those giving glicosilo will seek to ciclación intramolecular and stereoselective induced iodine electrófilo of polihidroxi-pentenilsulfuros and polihidroxi-hexenilsulfuros. This method would allow access to giving glicosilo giving with iodine in position 2 by a process that does not require from glicales. It has developed a new method of stereoselective synthesis of 2-desoxiglicósidos consisting of the use of phenyl 2-desoxi-2-yodo-1-tioglicósidos as giving glicosilo. The reaction glycosylation of different alcohols were carried out with excellent estereoselectividad and performance by activation of thioglycoside with NIS / TfOH. The phenyl 2-desoxi-2-yodo-1-tioglicósidos have been synthesized so by stereoselective reaction ciclación intramolecular of vinilsulfuros induced reactive iodine electrófilo. In turn the vinilsulfuros were obtained from pentosas by Wittig reaction olefinación type. The method is efficient for the synthesis of glycosides piranósidos, while it has proved unsuccessful in obtaining glycosides furanósidos since the ciclación intramolecular of vinilsufuros leads mainly to ciclación 6-endo to give rise to piranosas rather than 5-endo giving place furanosas. It has also studied the reactions of ciclación of hidroxi-enoléteres with reagents electrófilos fluoride, which have provided cyclical fluorinated compounds. So were obtained 2-etoxi-3-fluoro-benzotetrahidrofurano and 2-etoxi-3-fluoro-5-hidroximetiltetrahidrofurano, which can be considered as an 2-fluoro-furanósido precursos of 2-fluoro-nucleósidos.

Author: SALAS SOLANA JORGE.
Year: 2003.
University: BARCELONA.
Place of defense: QUÍMICA.
Place of preparation: J.URIACH & CÍA S.A..

Summary: Doctoral Thesis This is a work of applied research in the field of Medical Chemistry. It focuses on the study of the following GPIIB-IIIA And VLA-4, some cell adhesion receptor type protein, which have recently been validated as targets potentially terapéuticas.Por one hand antagonists of the integrina GPIIB-IIIA have demonstrated their effectiveness as potent antiplatelet and other antagonists of the VLA-4 may provide a new treatment in chronic inflammatory disease (multiple sclerosis, asthma or rheumatoid arthritis). The work is divided into two chapters independientes.En first arose optimizing the synthesis of acid 2 (S) - (bencenosulfonilamino) -3-[N-[[2 (- (4.4 '-bipiperidin-1- il) -4-isopropilitiazol-5-il] carbonil] amino] propionic or UR-12947.Este compound had been previously identified as a potent antagonist of integrina GPIIb-IIIA and was elected as a candidate for initiating clinical studies. This part have studied all the required responses pair prepare this compound and has finally managed to bring the synthesis for implementation in a pilot plant: have improved yields in all steps and has been prevented cromatografías.Finalmente also has perfected a method for separation of enentioisómeros through elctroforesis capillary to ensure the optical purity of the final product. In the second chapter, first have designed a series of new molecules with nature peptidomimético that could act as a potent antagonist of the VLA-4. East study seha made using techniques computational modeling molecular.Como result of this work was proposed synthesis computational molecular modeling. As a result of this work was suggested synthesis of 61 compounds devididos into three families: derived from glutamic acid, acid (S ) -2.3 - diaminopropiónico (DPA) and the serina.Se developed schemes convergent synthesis common for the first two families and an outline specific pair derivatives serine, and prepared all components pretendidos.En the specific case the ureas arising from the DPA has been developed, a new synthetic method for preparation from the opening nucleofílica of imidazolonas using radiation microondas.Finalmente all componpuestos have been assessed pharmacologically and has conducted a study estructuractividad (SAR) . In this study we have identified compounds with potent activity in vitro and antagonists of the VLA-4 and has been selected the most active pair initiate studies farmaconcinéticos.Además are reduced structural important facts that have enabled us to better understand the interción between the integrina VLA-4 and its natural ligand, VCAM-1.

Author: MBA BLҁZQUEZ MIRIAM.
Year: 2003.
University: COMPLUTENSE DE MADRID.
Place of defense: FACULTAD CIENCIAS QUҍMICAS.
Place of preparation: FAC, DE CIENCIAS QUҍMICAS.

Summary: This memory consists of two capÃÂtulos distinct. The first one describes the sÃÂntesis of ansa-bisindenilmetalocenos of tecnologÃÂa Repsol YPF of simetrÃÂa C2 and its evaluaciÃÂ charges as catalysts for obtenciÃÂ ³ n polypropylene isotÃÂ ¡tico.Por also describes a new metodologÃÂa which allows obtenciÃÂ charges of ciclopentadienos 1, 2.3, and 1,2,4 trisustituidos quite regioselectiva and from the same precursor: a 2-furilcarbinol. In the second capÃÂtulo have focused we have focused our atenciÃÂ charges in 4-hidroxiciclopentenonas and siliderivados.Se has begun to study their behavior versus reactive organometÃÂ ¡licos, which has enabled us to describe additions Region and esteroselectivas reagents aorganometÃÂ ¡licos, This has allowed us to describe the additions and esteroselectivos of regal and Grignard reagents organolÃÂticos on sustratos.Por other side has been implemented this metodologÃÂa to sÃÂntesis of ciclopentenonal with quaternary centers in alpha and the sÃÂntesis of (+) -Prelactona B as an example of a natural product that can be accessed.

Author: ORTEGA GUITIÉRREZ SILVIA.
Year: 2003.
University: COMPLUTENSE DE MADRID.
Place of defense: CIENCIAS QUÍMICAS.
Place of preparation: FACULTAD DE CIENCIAS QUÍMICAS.

Summary: This work has been Doctoral Thesis in the design, synthesis and development of new reuptake inhibitors of anandamide acid derivatives grasos.La majority of the synthesized compounds have shown a high afinidadd (IC50 = 25-0,8 UM) for inhibier the transport of anandamide, a result also selective for the rest of qu proteins are endogenous cannabinoid system (receptors CB1 and CB2 and enzyme FAAH), and receivers vanilloides VR1.El qualitative analysis of relationship estructura-afinidad has deepened in the structural requirements for optimal inhibition of the reuptake of anandamida.Este study has resulted in the identification of UCM707 as the more potent inhibitors (IC50 = 0.8 UM) and selective until fecha.Este promising profile in vitro UCM707 a valuable tool to study the process of reuptake of anandamide and assess their applicability terapéutica.Mediante employment UCM707 in neuronal cultures derived from mice FAAH- /-and FAAH + / +, has studied the contribution of the enzyme FAAH the process of reuptake anandamida.Este process is a complex phenomenon in which different proteins and, to a lesser extent, the mere dissemination through the membrana.Dentro the protein component, highlights the existence of an entity protein sensitive UCM707 which is responsible for approximately 50% of the internalization of anandamide and could correspond to a cytosolic protein carrier lipids. With regard to the applicability therapeutic UCM707 has shown that treatment with this compound produced significant benefits in the model for multiple sclerosis induced virus Theiler, greatly enhancing the motor dysfunction associated with the process of enfermedad.EL UCM707 causes a decrease in microglial reactivity, in the expression of MHC II and the rest of factors proinflamatorios produced by célulars microglial (NO synthesis, and expression of Inos interleukins IL-1B and IL-6), due to the fact that empowerment the UCM707 produces on the pitch cananbionoide endogenous.

Author: LARRAZ ZATARAIN ELENA.
Year: 2003.
University: COMPLUTENSE DE MADRID.
Place of defense: FACULTAD CC QUÍMICAS.
Place of preparation: INSTTITUTO DE CIENCIA Y TECNOLOGÍA DE POLÍMEROS (CSIC).

Summary: The polymer molecules are formed by one or more units repeated many times, with a broad spectrum of physical and chemical properties and consequently an polymers in their use as biomateriales.Un biomaterial is a material designed and used to make biomedical devices that interact with systems biológicos.Los polymers with biomedical applications are being widely used in medicine and surgery and have mumerosas applications such as suture material, regeneration of skin, heart valves, bone cements and reconstruction of joints, dental cements, etc.Un type compounds attractive the point of view of their application as polymeric biomaterials are systems anfilícos compounds which are characterized by having two means of affinity for nature diferente.Este kinds of materials are being used as drug delivery systems for controlled release, how components of membranes synthetic or semisinteticas, artificial skin and coatings, components of bone cements, hydrogels, etc.. The main purpose of this study was to obtain systems with properties anfilílicas for use in biomedical applications in the repair of soft tissue (intervertebrales disks) and hard (dental cements) This has been done by the synthesis of a new macromonómero MT matter anfifílico and has been studied their reactivity in processes copolymerization radically in order to design systems with polymer properties específicas.Así have been prepared formulations autocurables to repair discs intervertebrales dental cements and glass ionomer.

Author: CHIOVA MOURAD.
Year: 2003.
University: COMPLUTENSE DE MADRID.
Place of defense: CIENCIAS QUÍMICAS.
Place of preparation: FACULTAD DE CIENCIAS QUÍMICAS.

Summary: The present report explores the formation of cicloalquil and alquilpirimidinas through the reaction, which was developed in our working group, ketones, nitrilos and acetic tríflico. * The use of symmetrical linear aliphatic ketones and not symmetrical has enabled data collection through mechanistic analysis of the stabilities of you intermediate involved. The findings of this study have allowed obtaining regioselectiva of alquilpirimidinas. The synthesis procedure has been extended to obtaining cicloalquilpirimidinas polynuclear. * Obtaining 2,4-bismetilticociclobutal [d] pirimidinas allows the preparation of ciclobuta [d] -pirimidinas with very different functional groups. * Ciclobuta [d] pirimidinas are excellent harbingers of o-quinodimetanos pirimidínicos. The presence of groups with different characteristics enables modular electronic reactivity face filodienos in reaction Diels-Alder. * Adducts Diels-Alder obtained from filodienos classics can be funcionalizar by oxidation followed by different processes of displacement nucleófilo. * Ciclobuta [d] pirimidinas are some precursors excellent o-quinodimetanos pirimidínicos. His generation and reaction Diels-Alder with C60 so evident. It thus opens a new synthetic route for obtaining adducts pirimidínicos derived from C60. * The presence of groups Methylthio allows funcionalización of adducts pirimidínicos derived from C60 and the preparation of adducts impossible to obtain through direct. * The implementation of the 1H-RMN at different temperatures can be obtained data on the dynamic behavior of adducts of C60 funcionalizados.

Author: GIACALONE FRANCESCO.
Year: 2003.
University: COMPLUTENSE DE MADRID.
Place of preparation: DEPARTAMENTO DE QUÍMICA ORGÁNICA I.

Summary: This thesis is divided into three parts: 1-In Chapter 1 discusses the electrochemical synthesis and study of new materials derived from fullerene, both C60 and C70, for incorporation into cells fotovoltacias orgánics. Among these derivatives is a series of difenilmetanofullerenos (MSA), and two dimeros chiral of C60 derivatives 1.1 '-binaftilo. The results include a derivative that MSA has obtained a value of conversion efficiency of 2.3%, one of the highest values obtained so far with a "totally organic." 2-In Chapter 2 describes the synthesis of several triads Dador-espaciador-Aceptor in which it has used the [60] fullerene as electron acceptor, the TTF *- extended or tetrafnilporfirina zinc and as a giver of oligomers different length and constitutción systems spacers. The synthesis of these materials has been completed, on the one hand, the study by voltamperometrí cyclic electrochemical dissolution, and secondly, your studio fotofísico. This study has helped prove the existence of processes electronic transfer fotoinducida and thus its potential usefulness in preparing devices fotovoltacios. The determination of the effect of the distance between units giver and aceptora on the electronic transfer kinetics in states with separation of cargo has uncovered an interesting behavior cable molecular nano dimensions. 3-In Chapter 3 has been carried out the synthesis of a number of derivatives of thiophene monomers into those as a side chain remains of fullerene, antrauinona or TCAQ unit electroaceptora, which were subsequently formed the polymerised so-called "dual wire." The synthesis of these new materials have been supplemented by its spectroscopic study and fotofísico which reveal the presence of processes electronic transfer fotoinducida from the skeleton of polythiophene to the unit aceptora electron. Finally photovoltaic devices has been prepared using the copolymers synthesized as active layer.

Author: RAMIRO PÉREZ PEDRO.
Year: 2003.
University: COMPLUTENSE DE MADRID.
Place of defense: FACULTAD DE CC. QUÍMICAS.
Place of preparation: FACULTAD DE CIENCIAS QUÍMICAS.

Summary: The reaction of esters tiólicos both aliphatic and aromatic, with nitrilos leads to 4 - (alquiltio) pirimidinas and 4 - (feniltio) pirimidinas, with moderate to good yields. In turn, these compounds can lead easily to pirimidinas 4-funcionalizadas through an oxidation reaction and after displacement nucleófilo later. The use of thiocyanates of rent as nitrilos departure leads to obtaining the ditioimidocarbamatos of rent as a unique final product, rather than the corresponding tris (alquiltio) pirimidinas. When performing the reaction between esters tiólicos aromatic and nitrilos Benzyl, are isolated exclusively (4Z) -2-alquil-4-benciliden-4H-1, 3-benzotiazinas, with moderate yields. The reaction between methyl esters and thiocyanate yields 4-alcoxi-2, 6-bis (Methylthio) pirimidinas with moderate yields. Then, they can lead to the acquisition of derivatives pirimidínicos funcionalizados, through two consecutive processes of oxidation and replacement nucleófila. In some cases, next to the priimidinas, retrieving alcanoiltiocarbamatos of S-metilo. The reaction of lactones and nitrilos leads to the corresponding pirimidinas heterocyclic only when using *- valerolactona as composed carbonílico basis, in which case they produce 6,7-dihidro-5H-piranol [2, 3-d] pirimidinas 2 , 4-disustituidas with a modest performance. In addition, it accesses a simple way to derivatives difuncionalizados through oxidation and the subsequent reaction with different nucleotide. If used beta-propiolactona as reactive, other products are obtained as a result of the apaertura ring lactónico. The extension of the procedure to other ketones heterocyclic did not give the expected results: the reaction of the tetrahidro-4H-4-piranona and nitirlos led to obtaining 7,8-dihidro-5H-pirano [4,3-d] pirimidinas 2 , 4-disustituidas with a low yield, whereas when the reagent is the tetrahidro-4H-4-tiopiranona occurs autocondensación of ketone. The reaction of alpha (Methylthio) acetone and nitrilos gives lguar to 5-metil-4- (Methylthio) oxazoles with good yields. The use of dinitrilos allows prepare oxazoles doubles by this methodology. These oxazoles funcionalizados can lead to 4 - (metilsulfonil) oxazoles by oxidizing Methylthio group, as well as to oxazoles with the position 4 free through a desulfurization reaction. In addition, they can be used in the reaction of cicloadición Diels-Alder.

Author: FERNÁNDEZ TRILLO FRANCISCO.
Year: 2004.
University: SANTIAGO DE COMPOSTELA.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: This thesis has been developed synthetic routes for the preparation of various poliacetilenos of marine origin, isolated from sponges family Callyspongia including: 1 .- Summaries of Callyberina A through two routes converging alternatives that include as key stages coupling reactions crossfire catalyzed by Cu between alquinos terminals and yodoalquinos (Reaction Cadiot-Chodkiewicz) and cross-coupling reactions, catalyzed by Cu, Pd, among alquinos terminals and vinyl halides (Reaction Sonogashira) 2 .- Summaries of Callyberina B through a convergent path that includes as a final step in a acoplmiento catalyzed by Cu and Pd between a diino terminal and a vinyl bromide. 3 .- Summaries of Callyberina C through a convergent path that includes as a final step in the desplazamineto a triflato through a diino terminal. 4 .- Summaries of Siphonodiol through a convergent path that includes as a final step in a link catalyzed by Cu and Pd between a diino terminal and a vinyl bromide.

Author: FERNÁNDEZ LÓPEZ ISRAEL.
Year: 2004.
University: COMPLUTENSE DE MADRID.
Place of defense: FACULTAD DE CIENCIAS QUÍMICAS.
Place of preparation: FACULTAD DE CIENCIAS QUÍMICAS.

Summary: Work performed during the dissertation is part of the field of chemistry organometálica and its application to the development of new processes in organic synthesis. Specifically, this work has focused on the study of complex metal-carbeno type Fischer Group 6, substrates proven versatility in organic synthesis. The most significant aspects of this thesis are, broadly speaking, the following: * Study teórico-experimental the photochemical reactivity of complex metal-carbeno type Fischer. In this paper we have used methods for calculating advanced along with support pilot to determine the mechanism of the reaction of fotocarbonilación of these complexes, its photochemical reactivity face iminas (for the generation of Beta-lactamas) and the search for new alternative forms the photochemical reactivity. This work has led to the proposal of a general mechanism for the reaction of these complexes with iminas, discovering a process of reordering 1,3-metalotrópico (pretty common in the chemistry of these complexes). Finally, it was discovered a new form of photochemical reactivity consisting of a reordering 1,2-diotrópico type I which is compatible with all kinds of complex metal-carbeno Group 6. * Design, synthesis and study of the reactivity of new complexes metal-carbeno structures conformacionalmente retringidas. In this case, have been synthesized with different types of complex structures cilofánicas and macrocyclic difficult to obtain by conventional methods. The electrochemical properties and reactivity of these complexes including them into some leading candidates for future application in the field of supramolecular chemistry and materials science of new metal. * Study teórico-experimental the behavior of complex metal-carbono Fischer processes electronic transfer. In this study, it has been developed, a new methodology for the detection of complex metal-carbeno mono and polymetallic by Mass Spectroscopy. We have found that these complexes are not ionizan under conditions of routine ESI-MS, however, the addition of substrates electron donors, such as lahidroquinona or tetratiafulvaleno allows ionization and enables detection. Moreover, we have managed to demonstrate unequivocally the privacy of electronic transfer of this process.

Author: MARTIN-FONTECHA CORRALES M. MAR.
Year: 2004.
University: COMPLUTENSE DE MADRID.
Place of defense: MEDICINA.
Place of preparation: FACULTAD DE CIENCIAS QUÍMICAS.

Summary: The study of the photochemical reactivity of compounds 1,4-insaturados in the presence of electron donors sensitizers has allowed describe the first examples of transpositions of certain types *- methane taking place through aniones-radicales in critical condition. The irradiation 1-aza-1 ,4-dienos leads only to the goods transposition 1-aza-di- *- methane, however, in the case of composite carbonílicos beta gamma-insaturados are observed, along with products transposition oxa-di- *- methane (ODPM), other alternative routes for the development of aniones-radicales intermediates, which include processes Norrish Type I that lead to products descarbonilación and migration 1.3 of acilo, as well as ciclaciones 3-exo-trig resulting in ciclopropanoles so diastereoselectiva. These processes ciclación also occur when aniones-radicales of compounds carbonílicos beta gamma-insaturados are generated by thermal using Sml2 as a reducing agent. Under these conditions, the reaction is also diastereoselectiva and passes with good performance. The 1,4-dienos experiencing transposition di-*- methane via aniones-radicales and the dienos presenting atractores electron substituents at positions 1 or 5 system, there is a change in the regioquímica the transposition regard to the irradicación directly, which increases the usefulness of this synthetic reaction. On the other hand, the irradiation of ketones beta gamma-insaturadas acíclicas with substituents atractrores electron position gamma, has described the first examples of reactions ODPM and Norrish Type I, which takes place through the excited state of alqueno S2 (* -*) The results obtained in this thesis represent a major breakthrough in the understanding of the photochemical reactivity and thermal compounds 1,4-insaturados and open new lines of research in this area.

Author: PÉREZ GARCÍA XENXO.
Year: 2004.
University: SANTIAGO DE COMPOSTELA.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: Most of the biological functions played by vitamin D3 taking place through its active hormone form, the 1st ,25-dihidroxivitamina-D3. These features are biological homeostasis of calcium and phosphorus, but it has recently been discovered that vitamin D3 is involved in other processes such as cell differentiation and maturation processes antiproliferative, regulation of the immune system, etc.. El primer objetivo de esta tesis es la síntesis de una serie de análogos de la 1a,25-(OH)2-d3 de cadena lateral rígida o semirrígida con el hidroxilo orientado hacia la región que ocupa en el cristal de Moras con el doble propósito from: 1) whether the region defined by the glass is biologically active and 2) obtain analogues with selective properties, and consequently potential value terpéutico (cancer, psoriasis, osteoporosis, etc.). For a summary of these analogs has been Used: a) a coupling type Wittig-Horner generating system triénico of vitamin D, b) in the case of similar rigid coupling catalyzed by metals (Pd, Cu) for the synthesis of the side chain or in the delos case similar semirrígidos, a reaction aldólica to generate the ring adicional.Los biological tests done for the analogue side chain rigid demonstrated that they are capable of inducing gene transcription in cells from colon cancer in a similar order or higher than the introducing hormone calcitriol effects calcémicos chain much lower than that produced 1a, 25 - (OH) 2-D3-Las biological tests performed on the analog side chain semi-rigid indicate that these compounds have a low affinity enclace the VDR and LPD much less than the calcitriol.Sin however, have antiproliferative effects on cancer cells HL-60 much larger than the hormone. It is known that hydroxylation in position C24 is the first step in the metabolic degradation of the metabolites of vitaminaD3.Las biological functions of these metabolites have not been studied in detail because of the absence of synthetic methods adecuados.El second goal of this work was to develop a synthetic route for easy access and quick to such compuesto.Para this was raised as a key step to obtain dela estereoquímica carbon 24 reaction symmetrical between aldehísos and organometallic zinc. Catalizada by the aminoalcohol DAIB developed by Noyori and Oppolzer.Usando this methodology has been synthesized compounds tacalciltol and calcipotriel currently sell for the treatment of psoriasis, as well as others of a similar nature.

Author: SESMILO CARRASCO M. ESTHER.
Year: 2004.
University: COMPLUTENSE DE MADRID.
Place of defense: FACULTAD CC. QUÍMICAS.

Summary: This report describes a new approach to the synthesis of systems 1,3-diol based on the use of a coupling reaction reductive cruazdo among a group epoxide and a carbonyl group. The reaction has been successfully tested in substrates highly funcionalizados and enantioméricamente pure derived from carbohydrates. The first chapter gives results in the release intramolecular process and its application to the synthesis of 2-hidroximetilciclopentitoles complex and enantioméricamente cigars. In reducers metallic ensaydos (SmI2, [V2Cl3 (THF) 6] 2 [Zn2Cl6], Cp2TiCl), only complex Cp2TiCl led the carbocilos expected. The reaction of carbociclación passes in these complex systems with moderate yields, good diastereoselectividad and total regioselectividad. It has been shown that diastereoselectividad of carbociclación is independent of the estereoquímica of epoxide, which allows postulate a rate mechanism radicalario initiated by transfer monoelectrónica reducer metal on the epoxide group, similar to the one proposed by other authors for processes. The new link is formed exclusively with carbon-carbon carbon replaced most of the epoxide group. The second chapter describes the development of intermolecular version of the process and its application to the synthesis of C-glicósidos by reaction 1,2-anhidroazúcares with aldehydes and ketones. In this case, as seen in the version intramolecular process, diyoduro of samarium provides yields much higher than the complex Cp2TiCl. As in the case intramolecular, the reaction of reductive coupling passes with total regioselectividad, with good performance and soft conditions and is compatible with a wide range of protectors of hydroxyl groups such as esters, ethers benzyl and silil ethers. The diastereoselectividad process is high and complementary to other methods reductivos employees earlier in the synthesis d eC-glicósidos. Thus, acomplamiento with aldehydes leads preferably C-glicósidos configuration alpha C-1, while generating ketones exclusively C-glicósidos of configuraicón 1,2-trans. This difference between aldehydes and ketones has been attributed to a combination of effects estéricos and estereoeléctricos. The reaction takes place with moderate to good yields even in the presence of a large excess of H2O, which supports the radicalario the stage of formation of carbon-carbon link. The source of proton is, however, an effect on diastereoselectiva of reaction, favoring the formation of C-glicósidos 1,2-cis even if ketones. This has been attributed to the protonación the hydroxyl group at C-2 of radical anomérico intermediate.

Author: SUREDA FERNÁNDEZ TANIA.
Year: 2004.
University: BARCELONA.
Place of defense: UNIVERSIDAD DE BARCELONA.
Place of preparation: UNIVERSIDAD DE BARCELONA.

Summary: Cylas jormicarius elegantulus is one of the most devastating pests that attack the potato under natural conditions and storage, and consequently is one of the major limiting factors in the production of this crop. Losses caused by the insect reach between 60 and 97% of the harvest. The sex pheromone of C. F elegantulus was isolated and identified in 1986 as the (E) -2 - butenoato (Z) -3-dodecenilo. In this paper we study the composition feromonal insect's presence in Cuba and develops the synthesis of pheromone by methods estereoselectivos and estereoespecíficos well as its activity in laboratory and field. The study of the composition feromonal only been detected (E) -2-butenoato (Z) -3-dodecenilo as the only component of the sex pheromone after analysis of volatile virgin females by SPME (Solid Phase Microextraction). The synthesis of (Z) -3-dodecenol, alcohol precursor of natural attractant, has been carried out by different synthetic procedures including: a) reaction of Wittig's 3-hidroxipropilentrifenilfosforano with nonanal b) réacción of metilentrifenilfosforano with ethylene oxide followed by metalación "on the spot" and Wittig reaction with nonanal c) coupling reaction iodides vinyl containing an oxygenated properly protected in the form of metoximetil, tetrahidropiranil and tercbutildifenilsilil ether with a Grignard reagent in the presence of a palladium catalyst d) reaction Suzuki 'own iodides acid n-octilborónico in the presence of a catalyst of palladium or nickel, e) hydrogenation of stereoselective precursor acetilénico 3-dodecinol. Alcohol desired was obtained with a purity estereomérica Z / E higher than 99%. The esterification of alcohol to obtain the corresponding crotonato driving by reaction with classical chloride crotonilo and pyridine and also in softer conditions for reaction with crotonato vinyl in the presence of a lipase. As a result of these investigations has succeeded in obtaining the natural pheromone with good performance and high purity estereomérica. The activity of the synthetic pheromone has been tested in laboratory bioassays as electroantenograma (EAG) and an olfactómetro dual choice. Thus, it has been determined that the peak period of the males is between 4 and 8 h within the escotofase and that the activity of the synthetic pheromone is similar to the pheromone business. It has been shown in studies EAG that the role crotonato ((E) -2-butenoato) is absolutely essential for the activity. The synthetic pheromone is very active field trials and it has been found that the activity is directly related to the purity estereomérica Z, E of the active compound.

Author: LARROSA GUERRERO IGOR.
Year: 2004.
University: BARCELONA.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA , UNIVERSIDAD DE BARCELONA.

Summary: In nature abound natural products contained in its structure hetero oxygenated six members substituted carbonised in positions 1 and 5, which is known as Cglicósidos. One method widely used for the construction of these involves the addition of nucleotide on glicales in the presence of Lewis acid, generating one or two estereocentros (1 and 1 '), in a reaction C-glicosidación. It has been described as adding crotilsilanos aquirales and chiral on glicales can obtain the corresponding C-glicósidos relations diastereoméricas moderate to good. In these reactions the adducts obtained always presented estereoquímicas on (1, -1-5) sin-trans and anti-trans, so C1 'is determined by the crotilsilano and Cl by glical. In this thesis we have developed a methodology that allows the addition of enolatos titanium chiral arising from the (S) - and (R) -4-isopropil-N-propanoíl-l ,3-tiazolidin-2-tiona on a wide variety of glicales fetching corresponding C-glicósidos with high yields (usually between 70% and 99%) and diastereoselectividades (up to 99:1). This method makes it possible to obtain satisfactory three of the four diastereómeros possible by proper choice of settings enolato and substituyente at position 6 of glical. For example, substituted on C6 as OTBS, OBn, Hy groups rent lead to adducts sin-trans or anti-trans, according to the enantiomer of enolato used, while when the substituyente is OCOR can obtain adducts sin-trans or without - cis, according to the enantiomer of enolato. Furthermore, it has been shown that pseudoglicales (acetal semicíclicos to B unsaturated) are synthetic equivalent of glicales, greatly expanding the potential of the method, since it presents a number of ways to prepare it. The adutos of C-glicosidación obtained can be treated very mild reaction conditions that allow the removal (and subsequent recovery) chiral auxiliary, transforming them into compounds synthetically useful as the corresponding alcohols, esters or amides Moreover, it has shown there are two bridges hydrogen intramoleculares type C-RS AND C-RO in adducts of C-glicosidación based on spectroscopic techniques, X-ray diffraction theoretical calculations at a high level. Finally, it has described the synthesis of the fragment C1-C9 of salinomycin, an antibiotic known polyether type ionóforo in 11 stages with a synthetic overall performance of 26% from (S) -3 - benciloxi-2-metilpropanal . The key stage of this synthesis has involved the construction of stereoselective link C2-C3 through methodology C-glicosidación developed in this thesis, by adding enolato titanium derivative of (S) -4-isopropil-N-butanoíl-l , 3-tiazolidin-2-tiona a pseudoglical properly funcionalizado.

Author: MONERRIS MASCARÓ MANUEL.
Year: 2004.
University: BARCELONA.
Place of defense: FACULTAD DE FARMÁCIA.
Place of preparation: FACULTAD DE FARMACIA.

Summary: In this Doctoral Thesis have studied certain aspects of two synthetic methodologies generally high interest in the synthesis of nitrogen compounds containing heterocyclic structures not only simple but also more complex as those present in the alkaloids and other bioactive compounds. The first of these methodologies are based on the use of synthetic intermediates dihydropyridines as for the construction of dihydropyridines with a high degree of substitution. The main achievements in this context were: 1 .- The synthesis of 1,4-dihidropiridinas related structurally with nifedipine. 2 .- The synthesis of two false alkaloids, the structure of harmanil-dihidropiridina had been mistakenly attributed to the alkaloid lialina and liadina. 3 .- The development of a simple procedure for the preparation of piridinas 3.5-disustituidas and 4 .- The synthesis of alkaloid naftiridínico jasminina. Secondly, we have studied the possibility of a synthetic process based on a synthetic sequential reaction metilenación of N-acilamidas followed by a reaction metátesis intramolecular of enamidas resulting. The process has been implemented on a preliminary to the construction of hetero simple fused with benzene such as indoles and quinolinas.

Author: ATIENZA CASTELLANOS CARMEN M..
Year: 2004.
University: COMPLUTENSE DE MADRID.
Place of defense: FACULTAD DE QUIMICAS.
Place of preparation: UNIVERSIDAD AUTÓNOMA MADRID.

Summary: The results obtained in this Doctoral thesis can be summarized in the following points: Obtaining systems oligoméricos different length has allowed to carry out synthesis systems diméricos derived from C60 united covalentemente through such systems oligoméricos conjugados.La absence of interactions electronic between fragments electroactivos in critical condition has been confirmed by studying the electronic spectra and redox properties of dimers of C60.Además, Study fotofísico has revealed that the fagmento conjugated Central acts as an antenna in front of the light Just after the irradiation of them only there is a transfer of energy. The presence of double and triple links in bisendiienos has enabled the synthesis of a system tetra-fullerénico obtained through a quadruple reaction cicloadición 1,3-dipolar. Voltamperograma cyclic systems resulting shows the presence of three waves of oxidation for the fragment of p-feniletinileno.En regard to the reduction zone nine waves appear reduction, eight of which correspond to the units of C60 and the remaining portion oligomérico.Como happened in the previous case, the study fotofísico indicates behavior antenna unit oligomérica central and noted that only a transfer of power after irradiation. The sequential growth through reactions Sonogashira of p-feniletinilenos (OPEs) have developed the synthesis of a series of díadas C60-OPEs along with a new set of triads C60OPE-exTTF.Para these compounds, the study fotofísico indicates the existence of a process of electronic transfer fotoinducida generating a state with separation of charges.