ORGANOMETALIC

Author: GUIU ROZAS ESTER.
Year: 2003.
University: ROVIRA I VIRGILI.
Place of defense: QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: Over the past few years have increased efforts, both academic and industrial, to the development of methods for the production of chiral substances in the form enantioméricamente pure. The field of homogeneous catalysis enantioselectiva has progressed tremendously in the past 30 years from the discovery of new catalytic systems and the use of new and more sophisticated chiral ligands. The objective of this work is focused on obtaining chiral amines by asymmetric hydrogenation phase homogeneous iminas and enamidas using iridium and rhodium catalysts. The amines are chiral intermediates useful in the synthesis of pharmaceutical and agrochemical compounds. Thus arose the study and synthesis of new iridium and rhodium catalysts with modular N ligands and P-donores. In this thesis describes the synthesis of ligands N-donores with symmetry C1 and presenting basic structure as a ring of oxazolina or imidazolina and a second atom coordinating, sulfur and phosphorus. It also discussed the coordination of these lignados to iridium and its reactivity in the hydrogenation of iminas proquirales. It also describes the synthesis of a ligand P-donores, including the preparation of two families with phosphorus ligands skeleton of carbohydrate. These ligands have different functionality fosforadas eg fosfinitos i phosphites. The ligands phosphorus bidentados and monodentados based on the D-xilosa presented simétria C1. We also conducted a systematic study on the influence of electronic properties and estéricas of ligands, synthesized new ligands bidentados based on D-manitol symmetry C1 and symmetry C2, and ligands monodentados symmetry C1, incorporating structural fragments and electronically different . It also discussed the coordination of these ligands in iridium. Systems Go (I) and Rh (I) with ligands bidentados and monodentados P-donores were used in reducing iminas and enamidas.

Author: HUERTA LOPEZ MONICA.
Year: 2004.
University: OVIEDO.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: This report describes new applications synthetic samarium, diyoduro samarium and triyoduro samarium in organic chemistry. Over the Report is devoted special attention to diastereoselectividad that takes the processes described. The first chapter gives results obtained in the reaction of beta-eliminación applied to the synthesis of (Z) -alfa-cloroésteres, alpha beta-insaturados and ketones (E) -alfa, beta-insaturadas so diastereoselectiva. In the same chapter describes a synthesis one-pot (Z) -haluros vinyl also diastereoselectiva, generating diyoduro samarium spot from samarium powder and diyodometano. The second chapter describes two sequential reactions. The first of these allows synthesize an efficient esters 2,3-dideuterados from alfa-halo-beta-hidroxiésteres using samarium powdered diyodometano and water deuterada. The second reaction sequence contained in this chapter, we can transform approximate ciclopropanocabozamidas through a process of eliminación-ciclopropanación promoted by diyoduro samarium and carbenoides samarium (generated from samarium and diyodometano). The ciclopropanocarboxamidas synthesized were obtained as a single diastereosisómero. Finally, the third chapter is collected reactions Baylis-Hillman promoted by dioyoduro samarium. The adducts Baylis-Hillman are formed by coupling between 2-cloroésteres and 2-clorocetonas alpha beta-insaturados and composite carbonílicos (aldehydes and ketones), obtaining always Z isomers with high total diastereoselección.

Author: ALVAREZ PÉREZ MÓNICA.
Year: 2004.
University: OVIEDO.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: This report deals with the study of processes carried out in the presence of reagents based on cation bis (pyridine) yodonio (R), as well as changes in terpenos natural enantioméricamente cigars through different sequences presented as a common bond of a first step CH insertion into complex boroxicarbeno Fischer previously developed in our research group. In Chapter 1 describes the modification of terpenos through the sequence consisting of a first stage of integration CH complex boroxicarbeno and in a second phase Beta-yodofuncionalización. The second stage is promoted through you trafluroborato bis (pyridine) yodonio (I) with high selectivity facial. In chapter 2 is posing a new methodology based on cation bis (pyridine) yodonio (R) to carry out the reaction of beta-azidoyodación of olefins in response to the resurgence of interest in this process and in an attempt to resolve problems found with other methodologies, and expand the applications of reactive iodine. Chapter 3 contains the transformation of terpenos unsaturated aldehydes in presenting three rings and four stages, through the sequential execution of the process of integration in CH complex boroxicarbeno and fragmentation Grob catalysed acid compounds for insertion. Finally, in chapter 4 is a study of the ability of reagents based on cation bis (pyridine) yodonio (R) to promote reunification reactions, both compounds 1,2-difuncionalizados as olefins. Additionally, the new methodology is applied to the modification of terpenos that was previously submitted for processing by inserting CH complex boroxicarbeno.

Author: PORTOLES GARCIA RAUL.
Year: 2004.
University: JAUME I DE CASTELLON.
Place of defense: E.S. TECNOLOGIA Y CIENCIAS EXPERIMENTALES.
Place of preparation: E.S. TECNOLOGIA Y CIENCIAS EXPERIMENTALES.

Summary: In this thesis has been prepared nitronas from 3,4-O-isopropiliden-L-eritrulosa. It has explored the reactivity of the same compared to the reaction of addition of organometallic compounds. Have been obtained under certain conditions high diastereoselectividades for adding species nucleofílicas. The absolute configuration of diastereomers obtained has been carried out by X-ray diffraction techniques of monocristal through correlation with chemical compounds known structures and through spectroscopic studies of derivatives rigid. The addition of products have been transformed into a-alquil-N-acetoxi-a-aminoesteres and (R) -a-metilserina. Have also been studied reactions cicloadición 1,3-dipolares between nitronas (dipoles) and dipolarófilos different types of electronics.

Author: VAZ ARAÚJO BLEÉN.
Year: 2004.
University: VIGO.
Place of defense: FACULTAD DE QUÍMICAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: Carotenoids are the most abundant natural pigments, being largely responsible for the different colors that are found in nature. They are mainly composed of eight units isoprenoides united among themselves following the rule of union cabeza-cola, except in the center of the molecule, where this connection is reversed. All coratoneoides may be considered formally derived from the structure C40 easier, through a variety of changes, all of them being common to a string poliénica Central, which defines much of their characteristics. Because of its antioxidant power as well as their participation in processes of capturing energy from light and photoprotection, has raised the development of a synthetic methodology that enables first, the preparation of carotenoids symmetrical C40, using as a key stage training links Csp2-Csp2 in building complete skeleton of carotenoide. Then, based on the same principles synthetic be prepared carotenoids highly funcionalizados as peridinina and pirroxantina. During the development of both synthetic methodologies have been used various kinds of reactions catalyzed by Pd, as reactions Heck, Sonogashira, Stille and Suzuki, testing these tools in the construction synthetic d epolienos of high complexity. In order to achieve the synthesis of form estereocontrolada have also been used reactions with high selectivity, as are epoxidaciones asymmetrical Sharpless, olefinaciones Julia modified and reactions Mukaiyama extentidas. Also in the development of synthetic methodology have been explored various alternatives, using metátesis of olefins, Wittig reactions, reactions type Mitsunobu, carboaluminacionesâ | Finally has been demonstrating the applicability of the reactions catalyzed by Pd in the preparation of carotenoids, by optimizing the reaction conditions for obtaining highly complex compounds polyene. This work can move into a much broader project of building an artificial photosynthetic device simulating the process of photosynthesis, capturing energy-efficient transmission of light and the reaction center. This device is based on the complex PCP present in the dinoflagellate Amphidinium carterae, whose crystal structure reveals the presence of two protein domains in which they are immersed 4 units carotenoide (peridinina) and 1 unit porfirinato (chlorophyll). As a result, there has developed a methodology to the construction of porphyrins A2B2 meso replaced, using the Suzuki reaction as a key step in the funcionalización these porphyrins.

Author: BERNARDO DE LA RUA RAMÓN.
Year: 2004.
University: OVIEDO.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: The present report describes the results of the study of the reactivity of alcoxicarbenos Fischer with different enaminas. This work has led to the development of new reactions carbociclación. It has also designed an easy access to complex carbeno Fischer Group 6 is not stabilized by heteroatoms and has begun studying its reactivity. The first chapter covers the preparation of molecules with the skeleton of piperidina obtained through reactions cabrocilcación [3 +3] and [3 +2] alquenilcarbenos Fischer with enamina heterocíclica 1,2-dimetil- * 2-tetrahidropiridina . In the second chapter describes the reactivity of alquenil (alcoxi) carbenos Fischer with enaminas from ciclopentanona and cyclohexanone. This will go to Bicycle [3.2.1] octenonas, Bicycle [3.3.1] nonenonas and tricycle [3.3.0.02,8] octanos through reactions carbociclación beta, beta 'and alpha, beta, beta'. Using enaminas arising from (S) -2-metoximetilpirrolidina accessing these adducts with high enantiomeric purity. In addition, it includes a detailed proposal mechanistic approach based on the isolation and characterization of an intermediate reaction. The third chapter is devoted to exploring new complex carbeno Fischer not stabilized by heteroatoms with substituents rent or alquinilo. First, it describes the formation and characterization espectroscópica and chemical complexes Bicycle [3.2.1] octan-2-ilidencarbeno and alkyl (aril) carbenos simple. Finally, lists studies preeliminares formation and reactivity of complex alquinil (SJC) carbeno and dialquinilcarbeno Group 6. Presents reactions of interest, like inserting links in intermolecular CH not activated, and especially the ciclopropanación regió and diastereoselectiva of ciclopentadieno.

Author: MORENO MARTÍNEZ BENJAMÍN FRANCISCO.
Year: 2004.
University: ALICANTE.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: This memory comes on the preparation of compounds organolíticos funcionalizados and its reactivity face electrófilos. These intermediates were prepared by reductive opening of a series of ethers and tioéteres cyclical bencíclicos, using as agents litiación well in excess lithium and catidad catalytic agent areno electron transporter, or an amount estequiométrica of arenuro lithium. You can build this memory into three blocks Heterociclos benzocondensados. We have studied the siguietes aspects: a) new reaction conditions permitting decrease the amount of lithium in excess when it increases the scale of reaction b) reactivity of the compound organolíticos funcionalizados front electrófilos proestereogénicos c) regioquímica at the opening reductive the hetero not symmetrical replaced. The reaction of the compounds organolíticos (generated from the opening reducing fitalano (1) and isocromano (19)) with electrófilos like compounds carbonílicos and iminas leads to dioles or aminoalcoholes respectively hetero naflelénicos. This methodology allows introduce two electrófilos different in both positions bencílicas acting this heterocycle as a sintón 1,8-dianiónico of 1,8-dimetilnaflaleno, -Heterociclos binafílicos. We have studied the conditions of reaction at the opening reducing sulfur and oxygen hetero for mono and doble-funcionalización positions bencílicas. Under conditions of adequate reaction is possible to generate sintones 1,6-dianiónicos of 2,2-dimetil -1.1 -binaftilo (from the dihidrodinaftoxepina 66 and its analog sulfur 67), both in racemic form as chirality.

Author: MACIÁ RUIZ BEATRIZ.
Year: 2004.
University: ALICANTE.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: The report describes the synthesis and reactivity of compounds organolíticos generated by rupture carbono-heteroátomo using lithium and an amount in excess of catalytic areno 4.4 '-di-terc-butilbifenilo (DTBB). In Chapter 1 describes the reactions litiación of the (z) - (E) -1.2 bis (fenilsulfanil) eteno, leading, after a process of reductive double break of both groups fenilsulfanilo at sintón Formal 1, 2-dilitioeteno. They are under study the reactivity of the intermediate face different electrófilos well as estereoquímica that passes the process. In chapters 2.3 and 4 detailing the preparation of compounds organodilitiados through dual exchange cloro-litio from the corresponding starting materials di-chlorinated, and the results of their reactions with different electrófilos. Specifically, Chapter 2 describes the synthesis and reactivity of sintones 1,3-dilitiados to, a'-funcionalizados, bis (litiometil) sulfone and sulfoxide a (litometil), while chapter 3 refers to sintón 1 , 3-delitio-2-buteno and 3-litio-butenos 1-funcializados species 1,3-dilitiada and intermediate organolíticos g-funcionalizados respectively. Finally, Chapter 4 deals with the preparation and reactivity of sintón 1,5-dilitiado b.funcionalizado 2,6-bis (litiometil) pyridine. In chapter 5 gives results inthe process of opening lowering cis-y trans-2 ,3-difeniloxirano through litiación catalysed by DTBB in conditions Barbier, paying particular attention to the recativiedad of intermediate and the estereoquímica of process. Finally, you Chapter 6 examines the transposión (2.3) of Wittig from different alil chloromethyl ethers, generating anion precursor of the transposition by litiación lowering link carbono-cloro.

Author: BUENO PERISÉ AGUSTÍ.
Year: 2004.
University: BARCELONA.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA UNIVERSIDAD DE BARCELONA.

Author: PEREZ SANCHEZ IVAN.
Year: 2004.
University: OVIEDO.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Author: GARCIA MANCHEÑO OLGA.
Year: 2004.
University: AUTÓNOMA DE MADRID.
Place of defense: UNIVERSIDAD AUTONOMA DE MADRID.
Place of preparation: UNIVERSIDAD AUTONOMA DE MADRID.

Summary: In this Doctoral Thesis has developed a general method of synthesis of a range of structurally very varied chiral ligands with sulfur structure ferroceno 1,2-disustituido and coordination bidentada P, S, presenting exclusively quiralidad planar. The modular nature of our approach offers the possibility of changing the nature of the electronics and estérica substituents. Given the preliminary results of our research group, in this Doctoral Thesis has extended the applicability of these catalytic reactions catalyzed by metal transition training links CA and CX, such as the reaction of replacement alílica catalyzed by palladium and reactions Diels Alder and-aza Diels-Alder using metal complexes such as acid ligands Lewis catalíticos.En three transformations study has shown that the properties estéricas and electronic substitution on the phosphorus atom proved crucial in the reactivity and asymmetric induction obtained . Broadly has been found that the combination of a tioéter voluminous (group terc-butilsulfenilo) and a phosphine poor electrons [group a (p-fluorofenil) fosfino] or a bulky phosphine [group a (o-tolil) fosfino oa (1-naftil) fosfino] is the ideal replacement in the replacement arílica asymmetric reaction catalyzed by palladium acetate 1,3-difenil-2-propenilo. The fosfinas bulky provide the best results with nucleotide little bulky as bencilamina, while the fosfinas poor electrons are more reactive and effective nucleotide bulkier as malonate Dimethyl or ftalimiduro potásico.En reaction Diels-Alder standard between the ciclopentadieno and N-acriloiloxazolidinona complexes with palladium (II) provided the best levels of reactivity and enantioselectividad, resulting optimal combination of complex dicloropaladio (II) of the phosphine voluminous di (o-tolil) Phosphine and AgBF4. In this transformation the complex of copper (I) the same Phosphine provided the adduct Diels-Alder configuration opposite, although in this case the asymmetric induction was moderate. This opposite enantioselectividad generated by the complex of palladium (II) and copper (I) can be attributed to the different geometry around the metal. These complexes have been evaluated in a reaction much less explored in asymmetric catalysis and synthetic greatest potential: the reaction aza Diels-Alder between N-sulfonil aldiminas and dienos rich in electrons as dieno of Danishefsky.En this transformation complexes of copper (I) proved to be much higher than those of palladium (II) or platinum (II). In particular, the kind with phosphine voluminous bis (1-naftilo) (5.1 mol%), in combination with AgClO4 (10 mol%), provided levels of reactivity and enantioselectividad much higher than the rest of complex copper (I ) with different substitution in the atom fósforo.Este complex of copper (I) of the phosphine voluminous bis (1-naftilo) catalyzes the addition Mannich kind of dieno of Danishefsky a wide variety of N-sulfonil iminas, leading after addition TFA of the reaction flask to 2,3-dihidro-4-piridonas with good yields (50-90%) and high enantioselectividades (75-98% ee). The scope of the structural response is very broad, with enantioselectividad little dependent on the nature of the imina (arílica, alquenílica or alquílica), the group protective sulfonílico linked to nitrogen and the substitution in the dieno (28 different cases analyzed). The utility in asymmetric synthesis of this new strategy aza Diels-Alder catalytic reaction has been shown to the preparation of various alkaloids and related compounds, and particularly 8 stacable 2c5 synthesis estereodivergente of Lasubinas I and II from a common intermediate.

Author: ALCARAZO VELASCO MANUEL.
Year: 2004.
University: SEVILLA.
Place of defense: CENTRO DE INVESTIGACIONES CIENTIFICAS.
Place of preparation: INSTITUTO DE INVESTIGACIONES QUÍMICAS.

Summary: The homogeneous catalysis enantioselectiva seeking the synthesis of a possible only delos enantiomers in processes in which they are created new chiral compounds is an area of particular interest because many products necessary for the development of human activity are chiral, and only one of the enantiomers potential is what produces the desired activity, while the other tends to be a source of unwanted effects. Given the need for new efficient catalysts for industrial level, the synthesis of new chiral ligands is an area of special interest. So we ask objectives of this dissertation the synthesis of new ligands based on nitrogen and carbon from hydrazines chiral. As representatives of the first group sintetizamos bis-hidrazonas of glyoxal, while within the second group just carry synthesis carbenos N-Heterocíclicos N-dialquilamino replaced. The bis-hidrazonas of glyoxal were used as ligands in the reaction of Diels-Alder between N-acriloiloxaxolidinona and ciclopentadieno catalyzed by Cu (II). After optimization of the product results from cicloadición was obtained with a enantioselectividad of 95% and a yield of 90%. The conditions optimized for this reaction were used with other dienos obtained results that match or even improve the results described in these processes. From hydrazines was designed a new strategy of introducing quiralidad in carbenos -heterocíclicos based on the introduction of groups dialquilamino exocíclicos structures already known of these carbenos as are those of imidazolin-2-ilideno, imidazol-2-ilideno and triazol-5-ilideno. The change in donor capabilities of these carbons by the presence of groups dialquilamino was evaluated, as well as induction produced in the formation of the axles chiral C-Rh of metal complexes formed. Finally, we carry out the synthesis of a new family of carbenos N-heterocíclicos synthesized from the structure imidazo [1,5-a] piridinal. The carbenos free derivative of this ring were characterized and their donor properties evaluated. It also carried out the synthesis of metal compounds derived from these structures carbénicas in different positions heterocycle.

Author: BEHLOUL CHERIF.
Year: 2005.
University: ALICANTE.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: In this thesis is desdribe the reductive elimination of different groups protectors alcohols, amines and thiol using processes litiación catalysed by a areno. In Chapter II. 1 detailing the unprotected group tritilo (trifenilmetilo), which is frequently used for selective protection of primary alcohols and amines because of the impediments estéricos it creates. It examines the selectivity of the rupture X-tritilo (X = N, O, S) or molecules that have several of these groups. In Chapter II. 2 describes breaking the link X-silicio (X = N, O, S) in different alcohols, amines and thiol sililados. Using the methodology of litiación catalysed by a areno leads to a method of desililación in non-acidic conditions. It also explores the quimioselectividad process. Chapter II. 3 is about the lack of alcohols, amines and thiol groups protected by the type carbonate, carbamate and tiocarbonato respectively. Using the same methodology litiación, has been achieved elimininación of groups aliloxicarbonil (Alloc) benciloxicarbonil (Cbz) and tercbutoxicarbonil (Boc). In chapter II.4 detailing the break-lowering esters, amides and tioésteres derivatives of benzoic acid piválico and. In the latter case, has studied the effect of substituents on the aromatic ring.

Author: GUERRA NAVARRO FRANCISCO JAVIER.
Year: 2005.
University: CASTILLA-LA MANCHA.
Place of defense: FACULTAD DE CIENCIAS QUÍMICAS (CIUDAD REAL).
Place of preparation: FACULTAD DE CIENCIAS QUÍMICAS (CIUDAD REAL).

Summary: The complexes of transition metals containing ligands type gripper (pincer ligands) has fueled a growing interest given the high degree of stability that gives the simple link MF, as well as the change in the properties of metal ale be coordinated by a strong giver sigma . The pincer type ligands have one thing in common: the atom giver Central deligando clamp belongs to a ring of benzene (type XCX), or a ring pyridine (type XNX). This kind of complex, as shown in the memory, can be modified in various sites affecting their properties: the atoms that make up the gripper, atoms connecting the ends of the gripper with the aromatic ring, substituents on the ring, etc. . The first of these possibilities has been studied widely, leading to type ligands CCC CNC, CNS, NNN, NCN, PCP, CPN, OCO, SCS and SNS. The ligands type CNC CCC and are usually connected to the metal through carbenos generated from sales of imidazolio. Different metals such as palladium, plantino, nickel, iridium, tin, molybdenum, rhodium, osmium, ruthenium, cobalt and have been described in the bibliography in the formation of complexes with these ligands. Another chance to alter the ligand gripper is to create centers estereogénicos in spacers joining the ends of the gripper with the central atom. Substitutions in the aromatic ring provide an opportunity to anchor these ligands or other pincer complex molecules, already being described in the literature catalysts dendriméricos based on these complexes. On the other hand, the progress made in the synthesis of carbenos N-heterocíclcios (NHCs) has made these compounds ligands as versatile as are the fosfinas within chemistry organometálica. The coupling reactions of palladium and metastasis of olefins are two of the fields where these ligands experienced a greater increase. The ring 1H-1 ,2,4-triazol has proved to be a suitable system for the coordination of metals through its nitrogen piridínicos, as a precursor to carbenos N-heterocíclicos. In addition, the nitrogen in position 4, which is free in the caliper ligands as described, could be coordinated with new metals resulting in complex heterobimetálicos. In chapter 1 of the report gives an account of the first type gripper NCN ligands based triazole, and the formation of complexes with palladium (II). Also, in Chapter 3 has been obtained systems multicarbénicos from derivatives (1.1 ') -metilenbis (1H-1 ,2,4-triazol). The high stability of these compounds allows amendment in order to optimize their properties. The catalytic activity of most paladaciclos synthesized has been studied in the reaction of Mizoroki-Heck. On the other hand, in Chapter 3 summarizes various metalaciclos platinum endured various functional groups in the ring bencénico. Similarly, a study has been made of their absorption spectra in the region Ultravioleta-Visible. This part was conducted in the Debye Institute belonging to the University of Utrecht under the supervision of Prof.. Gerard van Koten and Dr. Gerard PM Van Link.

Author: JUAN GIL MOLTÓ.
Year: 2005.
University: ALICANTE.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD CIENCIAS.

Summary: The present report describes the synthesis of various palladium complexes derived from di (2-piridil) aminomethane from commercially available materials and their application as a catalyst in different reactions coupling carbono-carbono.En paragraph of General Background as discussed various coupling reactions catalyzed by palladium, as well as the most common catalysts used in this type of procesos.En the first chapter details the different complexes with palladium ligands pyridine in the existing literature as well as the preparation and characterization the catalysts derived from di (2-piridil) aminomethane and its support on a co-polímero of poliestireno-alt-anhídrido maleico.En The second chapter examines the catalytic activity of palladium complexes prepared in the preceding paragraph and its stability in reaction alquenilación of halides of arilo (reaction Mizoroki-Heck). The reaction can be carried out with iodides, chlorides and bromides of arilo, rich and poor electrons, organic solvents, and iodides and bromides arílicos water, both for obtaining various cinamatos and estilbenos, interesting products from the point of light industrial and farmacéutico.En the third chapter examines the effectiveness of complex paladados in reaction Suzuki-Miyaura applied to the synthesis of biarilos, very interesting pharmacological compounds through training links Csp2-Csp2 in aqueous medium. There have also been generated links Csp2-Csp3 acoplando acids alcanoborónicos with haloarenos water, or substrates alílicos and Benzyl acid arenoborónicos in aqueous mixtures obtained in this way the corresponding alquilarenos and diarilmetanos.En the fourth chapter presents the study on the catalytic activity the catalysts derived from di (2-piridil) aminomethane reactions coupling Csp2-Csp (reaction Cassar-Heck-Sonogashira), in both aqueous and organic solvents, and Csp-Csp (Glaser reaction rate) to obtain alquinos internal and diinos respectively. In the fifth chapter describes the couplings Csp2-Csp of sila-Sonogashira in the synthesis of acetilenos simétrica- and not symmetrically substituted, catalyzed by palladium complexes prepared, as well as PdCl2.En the sixth and final chapter, there is a comparison between the catalytic activity shown by the homogeneous catalysts prepared and heterogeneous supported his version on a co-polímero of poliestireno-alt-anhídrido Maleic modified in different carbon-carbon coupling reactions studied.

Author: BAEZA CARRATALÁ ALEJANDRO.
Year: 2005.
University: ALICANTE.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: The present report describes the synthesis and applications cianhidrinas O-protegidas racémicas and enantioméricamente enriquecidas.En Part One describes a short background bibliographic around the synthesis racemic and enantioselectiva of cianhidrinas free and O-protegidas, as well as some of synthetic and their applications according to which sets the objectives as detailed in paragraph II.En the third paragraph detailing the discussion sections comprising: First racemic describes the synthesis of cianhidrinas O-protegidas absentee solvent catalysed by trietilamina, with a very rapid reaction and does not require most of the final products of purification alguna.En Secondly described the asymmetric synthesis of cianhidrinas O-benzoiladas by adding cyanide to benzoyl aldehydes catalyzed by the catalytic system BINOLAM-Ti (IV) at room temperature retrievable the ligand BINOLAM after the reaction. Also provides a brief mechanistic study of the reacción.En Third is describing the first synthesis of cianhidrinas O-fosforiladas enantioméricamente enriched by the addition of cianofosfato Diethyl to aldehydes catalyzed by the system catalytic BINOLAM-AlCl at room temperature retrievable the ligand BINOLAM after obtaining reaction and high enantioselectividades in the reaction products. In addition there is a more comprehensive mechanistic study of the reaction based on calculations computacionales.En Fourthly describes synthetic applications of cianofosfatos chiral, deepening reactions replacement nucleofílica alílica catalysed or non-metal transition on cianhidrinas O-protegidas enantioméricamente enriched b g-insaturadas.Por finally reflected the experimental findings and annexes (Section IV, V and VI respectively).

Author: Rodríguez Garrido Nuria.
Year: 2005.
University: VALENCIA.
Place of defense: Facultat de Química.
Place of preparation: Facultat de Química.

Summary: The implementation of the transition metals in organic synthesis has experienced spectacular growth in the last thirty years, as the reactions catalyzed by these metals provide simple methods for the formation of carbon-carbon links and carbono-heteroátomo. (Ref.1) In this context, the cross-coupling reactions between organic halide or pseudohaluro (electrófilo) and a reactive organometálio (nucleófilo) catalyzed by palladium and nickel, occupy an important place. (Ref.1) The overall objectives of this report reflects the results of the study of the reactions catalyzed by palladium on carbon alpha in a group sulfinilo. At the beginning of this research, there was no precedent in the literature on this type of reactions so that the results offer a week of reactions catalyzed by palladium. The goals include both non-oxidative transformations (training links CA) as oxidative (oxidation of alcohols). 1 .- Transformations oxidative not. 1.1 .- Reactions arilación direct carbon in a group sulfinilo. A variant of the conventional cross-coupling reactions, the reaction is catalyzed by palladium coupling direct links with organic halides CH or heteroátomo-H, in the presence of a base. The main advantage of this method is the replacement of a reagent organometálico by a carbanión generated in situ in the reaction medium. (Ref.2) In this context, the study of the reactivity of alfa-sulfinil anion in the reaction of arilación direct catalyzed by palladium has led to the following conclusions: - The result of the reaction depends on the nature monodentada or the bidentada Phosphine used in the catalytic system. - If using a phosphine bidentada, the reaction catalysed leads to the formation of diaryl sulfóxidos reaction as a result of a coupling between a crossover halide arilo and acid sulfénico generated on the spot in the middle of reaction from -alfa sulfinil anion . The formation of diaryl sulfóxidos through a cross coupling reaction is unprecedented in the literature. The catalytic system with phosphine monodentada can be obtained product arilación direct albeit with poor performance. 1.2 .- Reactions Suzuki-Miyaura aimed at arilción carbon alpha in a group sulfinilo. A second approach to alfa-arilación of sulfóxidos through cross coupling reactions, is to use the sulfoxide as a component electrofílico (alfa-halosulfóxido). The method offers advantages complementary to approximate previous particularly when working with organometallic compounds of boron (like reactions Suzuki-Miyaura). These reagents are often used with mild reaction conditions are commercial and are manipulated easily compared with other organometallic compounds. Introducing the added advantage that they are thermally stable and inert to oxygen and water, so it can be used without taking special precautions. On the other hand, alfa-halo sulfóxidos not usually experience reactions replacement nucleofílica of halogen with nucleotide carbon. (Ref. 3) The carbaniones strong organometallic compounds such as magnesium and lithium, react with the sulfur atom displacement of anion of bromometilo (Ref. 4), while the least organometallic reagents such as zinc or boron not react . The lack of reactivity of alfa-halo sulfóxidos organometallic with boron or zinc makes them suitable candidates for use in reactions catalyzed by metal transition. The reaction described allows the replacement of halogen by a group arilo replaced with groups giving or aceptores in any position of the ring, in mild conditions and with re 8 ndimient ff8 will moderate to high. (Ref. 5) When the alfa-bromo sulfoxide is optically active, the transformation takes place without loss of optical activity. (Ref. 6) This increases the utility of synthetic procedure described as the chiral sulfóxidos chiral auxiliaries are commonly used in asymmetric synthesis. Likewise, the reaction also takes place with a alfa-bromo sulfoxide secondary. (Ref. 7) The cross-coupling reactions with halides side as substrates are quite unusual, since in these cases the reaction of beta-eliminación hydride is a significant competitive reaction. However, in our case, and possibly because of an effect conformacional derived from the presence of sulfoxide, the reaction of beta -eliminación was not a reaction secondary importance. On the other hand, success in this goal has allowed the development to turn the estereoquímica the reaction of cross coupling of halides on rent, in terms of a standard reaction Suzuki-Miyaura. 2 .- oxidative Transformations. 2.1 .- Reactions oxidation of alcohols. The development of oxidative processes has received less attention because of the need to use an oxidizer in quantities estequiométricas to regenerate the active catalytic species. In this sense, we have as an objective the development of a suitable catalyst system that would allow us to conduct the anaerobic oxidation of alcohols to the corresponding compounds carbonílicos. This catalytic system, deshalogenación of alfa-halo sulfoxide imply the regeneration of the active catalytic species of palladium. Thus, a system was developed that allowed catalytic conduct quimioselectivamente the anaerobic oxidation of alcohols alílicos and Benzyl where palladium catalysed be used alfa-bromosulfóxido as co-oxidante. (Ref. 8) The advantages of this method include:-Non sobre-oxidación of primary alcohols to carboxylic acids. - Tolerance of functional groups sensitive to oxygen-C = C, -SR and -NR2. The possible development of aldehydes and ketones alpha beta-insaturados result of the oxidation of alcohols alílicos primary and secondary. The reaction Heck with co-oxidante is not a reaction to our competitive system. References: Ref.1: a) Metal-Catalyzed Cross-Coupling Reactions Diederich, F.; Stang, P. J.; Wiley- VCH, New York, 1998. B) Reagents and Palladium Catalysts, Innovations in Organic Synthesis. Tsuji, J.; Wiley-VCH, New York, 1995. Ref.2: a) Satoh, T., Kawamura, Y.; Miura, M.; Appoints, M. Angew. Chem. Int. Ed. 1997, 36, 1740. B) Palucki, M.; Buchwald, S. L. J. Am. Chem. Soc. 1997, 119, 11108. C) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1997, 119, 12328. Ref. 3: Creary, X.; Mehrsheikh-Mohammadi, M. E.; Eggers, M. D. J. Am. Chem. Soc. 1987, 109, 2435. Ref. 4: Maseru, H.; Ryoichi, M.; Takeaki, S.; Kazuo, F.; Shunji, T. Synthesis 1977, 789. Ref. 5: Rodriguez, N.; Basin, A.; Ramirez de Arellano, C.; Medio-Simon, M.; Asensio, G. Org. Lett. 2003, 5, 1705. Ref. 6: Rodriguez, N.; Basin, A.; Ramirez de Arellano, C.; Medio-Simon, M.; Comb, D.; Asensio, G. J. Org. Chem. 2004, 69, 8070-8076. Ref. 7: Rodriguez, N.; Ramirez de Arellano, C.; Medio-Simon, M.; Asensio, G. In preparation. Ref. 8: Rodriguez, N.; Medio-Simon, M.; Asensio, G. In preparation.

Author: MORENO FLORES ROSA M..
Year: 2005.
University: BARCELONA.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA - UNIVERSIDAD DE BARCELONA.

Summary: There has been a synthesis of a family of beta-ferrocenil-beta-amino alcohols high enantiomeric purity. These compounds were obtained as a synthetic route generally whose key stage, which allows control estereoselectividad process is the reaction of dihidroxilación asymmetric Sharpless of ferrocenilalqueno appropriate. The beta-ferrocenil-beta-amino alcohols and synthesized products are taken as the basis for obtaining various ligands interest in asymmetric synthesis, such as ligands type 1,3-oxazolidin-2-ona or 1,3-oxazolina . It has implemented 4-ferrocenil-1 ,3-oxazolidin-2-ona as chiral auxiliary in methylation reactions diastereoselectivas and reactions cicloadición of Diels-Alder. It has also obtained a family of ligands form a (oxaxolina) and (difenilfosfinofenil) oxazolina and its complex derivatives alill palladium (II). These compounds have been successfully implemented in replacement alílica catalyzed reactions by palladium, however substitution in the carbon alpha amino alcohol is a key factor in controlling the mobility conformacional introducing the group ferrocenilo in such structures, and so able to obtain greater enantioselectividad in the final product. It also has developed a family of ligands types imina by direct condensation delos beta-ferrocenil-beta-amino alcohols starting with a derivative of salicilaldehido. These compounds have been used as ligands in various processes such as asymmetric catalysis in the addendum enantioselectiva cyanide trimetilsililo and diceteno to benzaldehido catalysed by titanium (IV). In this case different models have been proposed to justify enantioselectividad observed depending on the method of calculation by mechanical molecular SIBYL implemented in the software package SPARTAN. Again replacing carbon in the position of alpha amino alcohol is a factor in the enantioselectividad observed. Finally, within our interest in the synthesis enantioselectiva of new compounds derived from ferroceno, has created a synthetic route for obtaining for the first time a alfa-ferrocenil-alfa-aminoácido.

Author: NIETO OBERHUBER CRISTINA MONTSERRAT.
Year: 2005.
University: AUTÓNOMA DE MADRID.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: As a first objective of this dissertation, we set out to develop new complex Au (I) with different ligands, in order to find more complex reagents. Based on the results of reaction catolizadas by Pd, we decided to use fosfinas with ligands biphenyl (2a-d), and based on complex ligands N-heterocíclicos (3a-c). Also, we performed the preparation of the corresponding complexes catióniones (2e-f) in order to avoid the use of Ag (I). To determine the efficiency of these catalysts were tested in reactions known to our research group. The study of these reactions revealed that complexes with ligands fosfinas with biphenyls were the most active. In the case of the reaction of transposition of skeleton, these possible to carry on the reaction to -40Â ° C in just 3h, with excellent yields. In the case of the reaction of alcoxiciclación, reaction times were reduced at room temperature just 15 minutes in the case of alquenos more activated. With the aim of studying the selectivity of the new complexes are testing the reaction of bisciclopropanación. It can be concluded from this study that, in general and for most of the complex, tetraciclo 17 is obtained predominantly or almost exclusively with excellent yields and conversions, even at low temperatures. Using DFT calculations, the possible mechanisms have been proposed, which leads to the two tetraciclos with the opposite configuration around the second ciclopropano. After having examined the various complexes prepared, we made it our second objective of this dissertation, the search for new reactivity associated with eninos. When used a group arilo as replacement of alquino. In this case there is a ciclación similar causing 2,3,9,9 a-tetrahidro-1H-ciclopental [b] naphthalenes. The ciclación takes place differently replaced with arils and accepts both groups electrón-donadores as electrón-atracadores on the aromatic ring (Scheme IX). Eninos with alquenos disustituidos also lead to ciclación with good yields. When there are two positions on the reactive aromatic ring, there are two types of products and also have been observed for both types of ciclación possible endo-and exo. In the case of eninos with alquenos monosustituidos observed training Bicycle [3.2.0] heptenos. Mecanísticamente, the reaction takes place with the formation of ciclopropil carbeno XVII and opening it by aromatic ring via SEAr to generate XVIII. As a last objective of this dissertation we intended to study in detail the reaction of transposing skeleton. The new cationic complexes Au (I) 2e-f, have enabled us to carry out the reaction of transposition in a clean and quantitative even at low temperatures (-40Â ° C in 3h there is a higher than 98% conversion). This allowed us to track the reaction by 1H-RMN at different temperatures (between 210 and 254 K). An analysis of this reaction can obtain constant velocity at different temperatures, considering the reaction of pseudo-primer order. With the constant speed and applying the steady state theory developed by Eyring, got the activation parameters (Scheme XV). The DFT calculations made discarded the ciclobutenos as interim because they were not obtained in a straightforward way from ciclopropil-carbenos configuration anti (anti-17). However, when we analyze the ciclopropil-carbenos configuration syn (Syn- 117 ') if there is a direct way to obtain the ciclobutenos 122 routes TS11. But the formation of derivatives syn is significantly slower (Scheme XVI). The isomerization to anti-syn, requires a high activation energy due to the loss of conjutación between liaison cabénico and ciclopropano (Scheme XVIII). Although formaicón of carbeno anti-117 is more favorable, in certain cases, it may ocmpetir the ciclación via syn - 117 ', as is the case with 1,7-eninos where ciclobutenos are obtained on an exclusive basis. We can summarize the results obtained and 8 n pa 311 rai that the transposition of skeleton 1,6-eninos, competing three possible paths. In two cases the ciclación occurs via exo (anti-and syn) and the other via endo.

Author: MASLLORENS LLINÀS JUDIT.
Year: 2005.
University: GIRONA.
Place of defense: UNIVERSIDAD DE GIRONA.
Place of preparation: UNIVERSIDAD DE GIRONA.