Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations

Catalysis is a mature field with extensive practical applications in today's society.indeed,the catalysis of petroleum refining,fine chemical synthesis and emission control demands the production of catalysts in bulk quantities.Future improvement of these well established processes is likely to be incremental.On the other hand,the continuous demand for new products will require additional novel and innovative processes.The need for pollution abatement and prevention also imposes new demands on catalysis, and new processes are periodically advanced for the control of emission of gases as well as for remediation processes such as the cleaning of underground waters. The number of problems where catalysis can have a big impact is constantly growing.In general,science stimulated by the technology has enriched the field of catalysis in a way that has had broad and lasting value.The thesis"Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations" accounts the preparation and characterization studies of both transition metals and rare earth metals modified sol-gel titania and its applications in industrially useful organic reactions.

N-halossacarinas: reagentes úteis (e alternativos) em síntese orgânica

N-halosaccharins proved to be useful and alternative reagents for diverse organic transformations, such as halogenation of aromatic compounds, benzylic and alpha-carbonylic positions, cohalogenation of alkenes, oxidation of secondary alcohols, etc. Their preparation from saccharin, a cheap and readly available starting material, is simple.

Reações de organocatálise com aminas quirais: aspectos mecanísticos e aplicações em síntese orgânica

The philosophy of organocatalysis is based on the utilization of organic compounds to catalyze organic transformations without the intervention of metals. This area has attracted much attention of the synthetic chemistry community on the last years, which can be confirmed by the explosion of published papers dealing with this subject. Phosphorus compounds, urea and thiourea derivatives, alkaloids, guanidine derivatives, for example, have already been used as organocatalysts. In this review we have focused on the use of chiral amines as organocatalyst. We have also chosen some outstanding examples to demonstrate the potentiality of this strategy in the synthesis of natural products and biologically active compounds.

Experimental and Computational Studies on Copper and Hydrobenzoin Derivatives in Catalytic Asymmetric Reactions

The use of theory to understand and facilitate catalytic enantioselective organic transformations involving copper and hydrobenzoin derivatives is reported. Section A details the use of theory to predict, facilitate, and understand a copper promoted amino oxygenation reaction reported by Chemler et al. Using Density Functional Theory (DFT), employing the hybrid B3LYP functional and a LanL2DZ/6-31G(d) basis set, the mechanistic details were studied on a N-tosyl-o-allylaniline and a [alpha]-methyl-[gamma]-alkenyl sulfonamide substrate. The results suggest the N-C bond formation proceeds via a cisaminocupration, and not through a radical-type mechanism. Additionally, the origin of diastereoselection observed with [alpha]-methyl-[gamma]-alkenyl sulfonamide arises from avoidance of unfavourable steric interactions between the methyl substituent and the N -protecting group. Section B details the computationally guided, experimental investigation of two hydrobenzoin derivatives as ligands/ catalysts, as well as the attempted synthesis of a third hydrobenzoin derivative. The bis-boronic acid derived from hydrobenzoin was successful as a Lewis acid catalyst in the Bignielli reaction and the Conia ene reaction, but provided only racemic products. The chiral diol derived from hydrobenzoin successfully increased the rate of the addition of diethyl zinc to benzaldehyde in the presence of titanium tetraisopropoxide, however poor enantioinduction was obseverved. Notably, the observed reactivity was successfully predicted by theoretical calculations.

High-Spin and Emissive Molecular Materials: Synthesis and Characterization of New Polynuclear Ni(II) Complexes from the Use of Aromatic Schiff Bases as Bridging Ligands

The employment of the bridging/chelating Schiff bases, N-salicylidene-4-methyl-o-aminophenol (samphH2) and N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in nickel cluster chemistry has afforded eight polynuclear Ni(II) complexes with new structural motifs, interesting magnetic and optical properties, and unexpected organic ligand transformations. In the present thesis, Chapter 1 deals with all the fundamental aspects of polynuclear metal complexes, molecular magnetism and optics, while research results are reported in Chapters 2 and 3. In the first project (Chapter 2), I investigated the coordination chemistry of the organic chelating/bridging ligand, N-salicylidene-4-methyl-o-aminophenol (samphH2). The general NiII/tBuCO2-/samphH2 reaction system afforded two new tetranuclear NiII clusters, namely [Ni4(samph)4(EtOH)4] (1) and [Ni4(samph)4(DMF)2] (2), with different structural motifs. Complex 1 possessed a cubane core while in complex 2 the four NiII ions were located at the four vertices of a defective dicubane. The nature of the organic solvent was found to be of pivotal importance, leading to compounds with the same nuclearity, but different structural topologies and magnetic properties. The second project, the results of which are summarized in Chapter 3, included the systematic study of a new optically-active Schiff base ligand, N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in NiII cluster chemistry. Various reactions between NiX2 (X- = inorganic anions) and nacbH2 were performed under basic conditions to yield six new polynuclear NiII complexes, namely (NHEt3)[Ni12(nacb)12(H2O)4](ClO4) (3), (NHEt3)2[Ni5(nacb)4(L)(LH)2(MeOH)] (4), [Ni5(OH)2(nacb)4(DMF)4] (5), [Ni5(OMe)Cl(nacb)4(MeOH)3(MeCN)] (6), (NHEt3)2[Ni6(OH)2(nacb)6(H2O)4] (7), and [Ni6(nacb)6(H2O)3(MeOH)6] (8). The nature of the solvent, the inorganic anion, X-, and the organic base were all found to be of critical importance, leading to products with different structural topologies and nuclearities (i.e., {Ni5}, {Ni6} and {Ni12}). Magnetic studies on all synthesized complexes revealed an overall ferromagnetic behavior for complexes 4 and 8, with the remaining complexes being dominated by antiferromagnetic exchange interactions. In order to assess the optical efficiency of the organic ligand when bound to the metal centers, photoluminescence studies were performed on all synthesized compounds. Complexes 4 and 5 show strong emission in the visible region of the electromagnetic spectrum. Finally, the ligand nacbH2 allowed for some unexpected organic transformations to occur; for instance, the pentanuclear compound 5 comprises both nacb2- groups and a new organic chelate, namely the anion of 5-chloro-2-[(3-hydroxy-4-oxo-1,4-dihydronaphthalen-1-yl)amino]benzoic acid. In the last section of this thesis, an attempt to compare the NiII cluster chemistry of the N-naphthalidene-2-amino-5-chlorobenzoic acid ligand with that of the structurally similar but less bulky, N-salicylidene-2-amino-5-chlorobenzoic acid (sacbH2), was made.

El análisis regional en la Argentina : Enfoque teórico-metodológico y aportes para su profundización

El artículo presenta los principales núcleos del enfoque de análisis regional en la Argentina, realizando distintos aportes a su desarrollo sobre las dinámicas de acumulación y hegemonía. En ese sentido, retomamos a autores como Rofman, de Jong y Levín, para comprender la relación entre territorio y sociedad. Partimos del planteo de construcción de conocimiento sintético y holístico, tratando de integrar las distintas escalas del análisis espacial con sus particularidades y sus interpenetraciones. La relación espacio/modo de producción nos lleva a la pregunta por las transformaciones orgánicas del capital como relación social y, así, al estudio del proceso de reproducción ampliada del capital a partir de conceptos como el de régimen y modelo de acumulación, a diferentes escalas, alcances y niveles de abstracción. Vemos las relaciones de fuerzas a nivel internacional a la luz de la disputa por distintos monopolios estratégicos, que señala Amín, y del lugar de las corporaciones transnacionales como agentes centrales de los regímenes de acumulación actual. En ese punto, continuamos desarrollando el plan de análisis de relaciones de fuerzas gramsciano, desde su nivel estructural hasta el momento de la hegemonía. De esta manera, la construcción del territorio dentro de una formación social nacional lleva a indagar la dinámica del proceso productivo, sus agentes, fracciones y clases, así como el rol del Estado y de la disputa entre distintos proyectos societarios. Estas dimensiones aparecen, asimismo, conjugadas, en una escala menor, en el análisis de los subsistemas espaciales de acumulación y de los circuitos productivos regionales que los constituyen. La explicitación de diversas claves teórico-metodológicas aparece atravesada por el debate en torno a repensar la planificación del espacio social, preguntándonos ¿qué territorio para qué sociedad?

El análisis regional en la Argentina : Enfoque teórico-metodológico y aportes para su profundización

El artículo presenta los principales núcleos del enfoque de análisis regional en la Argentina, realizando distintos aportes a su desarrollo sobre las dinámicas de acumulación y hegemonía. En ese sentido, retomamos a autores como Rofman, de Jong y Levín, para comprender la relación entre territorio y sociedad. Partimos del planteo de construcción de conocimiento sintético y holístico, tratando de integrar las distintas escalas del análisis espacial con sus particularidades y sus interpenetraciones. La relación espacio/modo de producción nos lleva a la pregunta por las transformaciones orgánicas del capital como relación social y, así, al estudio del proceso de reproducción ampliada del capital a partir de conceptos como el de régimen y modelo de acumulación, a diferentes escalas, alcances y niveles de abstracción. Vemos las relaciones de fuerzas a nivel internacional a la luz de la disputa por distintos monopolios estratégicos, que señala Amín, y del lugar de las corporaciones transnacionales como agentes centrales de los regímenes de acumulación actual. En ese punto, continuamos desarrollando el plan de análisis de relaciones de fuerzas gramsciano, desde su nivel estructural hasta el momento de la hegemonía. De esta manera, la construcción del territorio dentro de una formación social nacional lleva a indagar la dinámica del proceso productivo, sus agentes, fracciones y clases, así como el rol del Estado y de la disputa entre distintos proyectos societarios. Estas dimensiones aparecen, asimismo, conjugadas, en una escala menor, en el análisis de los subsistemas espaciales de acumulación y de los circuitos productivos regionales que los constituyen. La explicitación de diversas claves teórico-metodológicas aparece atravesada por el debate en torno a repensar la planificación del espacio social, preguntándonos ¿qué territorio para qué sociedad?

El análisis regional en la Argentina : Enfoque teórico-metodológico y aportes para su profundización

El artículo presenta los principales núcleos del enfoque de análisis regional en la Argentina, realizando distintos aportes a su desarrollo sobre las dinámicas de acumulación y hegemonía. En ese sentido, retomamos a autores como Rofman, de Jong y Levín, para comprender la relación entre territorio y sociedad. Partimos del planteo de construcción de conocimiento sintético y holístico, tratando de integrar las distintas escalas del análisis espacial con sus particularidades y sus interpenetraciones. La relación espacio/modo de producción nos lleva a la pregunta por las transformaciones orgánicas del capital como relación social y, así, al estudio del proceso de reproducción ampliada del capital a partir de conceptos como el de régimen y modelo de acumulación, a diferentes escalas, alcances y niveles de abstracción. Vemos las relaciones de fuerzas a nivel internacional a la luz de la disputa por distintos monopolios estratégicos, que señala Amín, y del lugar de las corporaciones transnacionales como agentes centrales de los regímenes de acumulación actual. En ese punto, continuamos desarrollando el plan de análisis de relaciones de fuerzas gramsciano, desde su nivel estructural hasta el momento de la hegemonía. De esta manera, la construcción del territorio dentro de una formación social nacional lleva a indagar la dinámica del proceso productivo, sus agentes, fracciones y clases, así como el rol del Estado y de la disputa entre distintos proyectos societarios. Estas dimensiones aparecen, asimismo, conjugadas, en una escala menor, en el análisis de los subsistemas espaciales de acumulación y de los circuitos productivos regionales que los constituyen. La explicitación de diversas claves teórico-metodológicas aparece atravesada por el debate en torno a repensar la planificación del espacio social, preguntándonos ¿qué territorio para qué sociedad?

Solvent- and Ligand-free Diboration of Alkynes and Alkenes Catalyzed by Platinum Nanoparticles on Titania

Platinum nanoparticles supported on titania efficiently catalyzed the diboration of alkynes and alkenes under solvent- and ligand-free conditions in air. The cis-1,2-diborylalkenes and 1,2-diborylalkanes were obtained in moderate to excellent yields following, in most cases, a simple filtration workup protocol. The versatility of the cis-1,2-diboronvinyl compounds was demonstrated in a series of organic transformations, including the Suzuki–Miyaura cross coupling and the boron–halogen exchange.

Solvent-Free Enantioselective Organocatalyzed Aldol Reactions

The use of proline as catalyst for the aldol process has given a boost to the development of organocatalysis as a research area. Since then, a plethora of organocatalysts of diverse structures have been developed for this and other organic transformations under different reaction conditions. The use of an organic molecule as catalyst to promote a reaction meets several principles of Green Chemistry. The implementation of solvent-free methodologies to carry out the aldol reaction was soon envisaged. These solvent-free processes can be performed using conventional magnetic stirring or applying ball milling techniques and are even compatible with the use of supported organocatalysts as promoters, which allows the recovery and reuse of the organocatalysts. In addition, other advantages such as the reduction of the required amount of nucleophile and the acceleration of the reaction are accomplished by using solvent-free conditions leading to a “greener” and more sustainable process.

Pursuing Chemical Efficiency by Using Supported Organocatalysts for Asymmetric Reactions under Aqueous Conditions

Over the past decade, a great effort has been made by the chemical community to improve the efficiency of organic transformations and allow sustainable processes. Merging the use of supported and recyclable organocatalysts and aqueous conditions for the asymmetric synthesis of valuable molecules, has led to outstanding contributions in the area of green chemistry. Recent progresses in the field include the implementation of these methodologies in the large scale production of chiral molecules using automated flow chemistry.

The synthesis and application of room temperature ionic liquids

This research project is concerned with the development and use of eco-friendly reaction media for a variety of organic transformations in the preparation of organic chemicals with potential pharmaceutical applications. These chemicals will then be investigated for their anti-cancer, anti-bacterial and anti-inflammation properties. In this project, different methods were used to synthesize various kinds of ionic liquids. Some new ionic liquids were prepared. In addition, Knoevenagel condensation reactions were investigated in RTILs. For the first time, some neutral ionic liquids such as [BMIM]+[BF4]-, [MeOEtMIM]+[CF3COO]- acted as both catalysts and solvents to promote Knoevenagel reactions. All these experiments indicated that RTILs have a great potential as alternative solvents in synthetic chemistry. Furthermore, nucleoside chemistry is an important research area in drug discovery. Various chemical modified nucleosides have therapeutic activities. However, these compounds usually have poor solubility in common organic solvents. RTILs such as [MeOEtMIM]+[CH3SO3]- have good dissolving capability for these chemicals. A range of thio-substituted nucleobases and nucleosides with potential pharmaceutical applications have been synthesized in several RTILs. These chemicals will then be investigated for their anti-cancer properties.

Sol-gel sulfonic acid silicas as catalysts

Silica-supported sulfonic acids are a class of solid Brønsted acid catalysts that generally comprise organo-sulfonic acid groups tethered to silica surfaces. Methodologies to prepare organically modified silica have been widely developed in separation science and the techniques for their preparation are well documented. The application of this chemistry to prepare pure Brønsted sulfonic acid functionalized mesoporous silicas has stimulated significant research effort in this area, since these materials are interesting alternatives to commercially available sulfonated polymer resins, such as Amberlyst–15 and Nafion-H (sulfonated polystyrene and perfluorinated sulfonic acid resins respectively), which suffer from low surface areas and thermal stability. This chapter presents an overview of the preparation of mesostructured silica supported sulfonic acids, their catalytic applications and reviews the approaches taken to tune catalyst performance in organic transformations.

Transformations in occluded light fraction organic matter in a clayey oxisol: evidence from 13C-CPMAS-NMR and delta13C Signature

We hypothesised that, during occlusion inside granular aggregates of oxide-rich soils, the light fraction organic matter would undergo a strong process of decomposition, either due to the slow process of aggregate formation and stabilisation or due to digestion in the macro- and meso-fauna guts. This process would favour the accumulation of recalcitrant materials inside aggregates. The aim of this study was to compare the dynamics and the chemical composition of free and occluded light fraction organic matter in a natural cerrado vegetation (woodland savannah) and a nearby pasture (Brachiaria spp.) to elucidate the transformations during occlusion of light fraction in aggregates of a clayey Oxisol. Nuclear Magnetic Resonance of the 13C, with Cross Polarisation and Magic Angle Spinning (13C-CPMAS-NMR), and 13C/12C isotopic ratio were combined to study organic matter composition and changes in carbon dynamics, respectively. The occluded light fraction had a slower turnover than the free light fraction and the heavy fraction. Organic matter in the occluded fraction also showed a higher degree of decomposition. The results confirm that processes of soil organic matter occlusion in the typical "very fine strong granular" structure of the studied oxide-rich soil led to an intense transformation, selectively preserving stable organic matter. The small amount of organic material stored as occluded light faction, as well as its stability, suggests that this is not an important or manageable sink for sequestration of atmospheric CO2.