No description available.

Au cours de ce travail, nous avons synthétisé des lactones bicycliques par réactions de Diels-Alder à demande électronique inverse, de façon énantio- ou diastéréosélective. Pour cela, nous avons étudié, d'une part, un système catalytique à base de triflate d'ytterbium utilisant le binol comme source de chiralité. Nous avons également étudié les cycloadditions d'une 2-pyrone portant une copule chirale dérivée de la pantalactone. Nous avons également découvert et développé un réarrangement radicalaire original de bicyclo[2.2.2]lactones substituées par un groupe phénylséléniure. L'étude du mécanisme de ce réarrangement nous a conduit à la production des lactones pontées [3,2,1], intermédiaires instables qui se transforment rapidement, sous conditions acides, dans les produits fusionnés correspondants. Nous avons ensuite étendu ces conditions à divers substrats et avons démontré que ce réarrangement procédait avec une rétention totale de la stéréochimie relative et absolue de la lactone de départ. Nous avons ensuite utilisé cette séquence tandem de réarrangement dans une courte synthèse de la lactone de Corey, intermédiaire important dans la préparation des prostaglandines.

Les prostaglandines (PG) jouent un rôle clé dans la régulation de la prolifération cellulaire, la différenciation et la régénération dans les systèmes gastro-intestinaux et cardio-vasculaires, et les réponses inflammatoires et immunitaires. Après un demi-siècle de développement, il a été démontré que PGs ont un large éventail de puissantes propriétés pharmacologiques sur l'inflammation, le glaucome, l'ostéoporose, le cancer, le diabète de type 2 et les maladies neuro-dégénératives. Les structures intéressantes et complexes de la PG et de leur disponibilité très limitée dans la nature ont suscité des chimistes organiques pour créer des méthodes de synthèse les plus élégantes afin de répondre à la recherche scientifique et les exigences pharmaceutiques. Dans cette thèse, nous avons réalisé la synthèse totale de la prostaglandine E2 (PGE2) en 24 étapes avec un rendement total de 1,33%, avec seulement 5 purifications chromatographiques pour l'ensemble du processus. Une synthèse efficace en one-pot des lactones de Corey a été mise au point à partir des dérivés chloro-cétoacide, en présence d'Oxone. Une méthode pratique pour la résolution racémique de l’acide 2-oxotricyclo [2.2.1.03,5]heptane-7-carboxylique avec haute valeur e.e. (> 99%) a également été développée. Les acides nucléiques et les glucides sont présents dans tous les systèmes vivants et jouent des rôles très importants en biologie comme l'expression des gènes et des processus de reconnaissance intracellulaires. Beaucoup d’efforts récents ont été consacrés au développement de mimes d'oligosaccharides et d’oligonucléotides synthétiques pour diverses applications biologiques, thérapeutiques et diagnostiques. Dans cette thèse, nous avons décrit la synthèse d'une nouvelle série d’oligosaccharides et d’oligonucléotide liés par des liaisons N-oxyamide. A partir de la diacétone D-glucose, les D-ribofuranoid glycoaminooxy acides ont été préparés comme une nouvelle famille de briques constitutives de sucre. Des homo-oligomères (de dimères à l'hexamère) ont été générés en tant que mimes d'oligosaccharides. Les nucléosides aminooxy acides ont été synthétisés pour la première fois, via la N-glycosylation des glycoaminooxy acides avec les cinq bases nucléiques. Le couplage entre les nucleosides aminooxy acides conduit aux dinucléosides liés par une liaison N-oxyamide. / Prostaglandins (PGs) play key roles in the regulation of cell proliferation, differentiation, and regeneration in gastrointestinal and cardiovascular systems, and a fundamental role in inflammatory and immune responses. After half century of development, PGs have been demonstrated to have a wide range of potent pharmacological properties on inflammation, glaucoma, osteoporosis, cancer, type 2 diabetes and neurodegenerative disorders. The interesting and complex structures of PGs and their very limited availability in nature have sparked the organic chemists to create more elegant synthesis methods to meet the scientific research and pharmaceutical demands. In this thesis, we have realized the total synthesis of prostaglandin E2 (PGE2) in 24 steps with a total yield of 1.33%, with only 5 chromatographic purifications for the whole process. An efficient one-pot synthesis of Corey lactones have been realized from the chloro-ketoacid derivatives in the presence of Oxone. A practical method for the resolution of racemic 2-oxotricyclo[2.2.1.03,5]heptane-7-carboxylic acid with high e.e. value (> 99%) has also been developed. Nucleic acids and carbohydrates are existing in all the living systems and play very important biological roles as gene expression and intracellular recognition processes. Much recent efforts have been devoted to the development of oligosaccharide mimetics and synthetic oligonucleotides for various biological, therapeutic and diagnostic applications. In this thesis, we have described the synthesis of a new series of N-oxyamide linked oligosaccharide and oligonucleotide mimetics. From the readily available diacetone D-glucose, D-ribofuranoid glycoaminooxy acid derivatives have been successfully prepared as a novel family of sugar building blocks. Homo-oligomers (dimer to hexamer) have been generated as oligosaccharide mimetics. Nucleoside aminooxy acids have been synthesized for the first time by N-glycosylation of sugar aminooxy acids with five common nucleic bases. Coupling reaction of nucleoside aminooxy acid derivatives furnished the desired N-oxy amide-linked dinucleosides.

Abstract The first part of this monograph discusses the asymmetric, ylide based, reagent controlled epoxidations. Both different chiral ylides and epoxidation processes, stoichiometric and catalytic, are reviewed. In the following part, new chiral sulfide catalysts were discovered as enantioselective catalysts for the Corey-Chaykovsky reaction (epoxidation of aldehydes via sulfonium ylides). Using a crystal structure of an oxazolidine derivative as a starting point, a thiazolidine ligand family was designed, synthesized and finally employed as catalysts in the asymmetric epoxidation of benzaldehyde. The ligands were prepared starting from L-valine, L-tert-leucine, D-penicillamine and L-cysteine. The differently tuned thiazolidine ligands were demonstrated to catalyze the formation of trans-stilbene oxide with varying enantioselectivities. On the basis of these results, a mechanistic rationale for the asymmetric induction was presented. The results heavily demonstrated the importance of ring rigidity as an affecting factor in the enantioselectivity of the tested thiazolidines.

No description available.

Thesis (M.M.)--Bowling Green State University, 2006. / Document formatted into pages; contains ix, 148 p. : music. Includes score: Coffin hollow / J. Corey Knoll. For alto flute, clarinet in B♭, percussion, piano, violin and violoncello. Includes bibliographical references.

Cílem práce je hodnocení ekonomické efektivnosti projektu výroby Corey Alkoholu ve firmě Cayman Pharma. Práce si klade za cíl vybrat ze tří resp. čtyř dostupných metod výroby Corey Alkoholu metodu takovou, která zajistí výrobu požadovaného množství Corey Alkoholu při minimální současné hodnotě nákladů a při rozumné míře rizika s ní spojeného. Cílem práce je tedy zvolení a doporučení jedné metody (jedné varianty projektu) k realizaci.

This thesis deals with direct and indirect determination of soil hydraulic characteristics (retention curve and hydraulic conductivity) in the locality of Bohaté Málkovice. For laboratory determination of soil moisture retention curve is used sand tank and pressure relief device. For the indirect determination of soil hydraulic characteristics is used computer software Rosetta, which includes 5 models of pedotransfer functions. For estimatiton of retention curves are applied previously derived pedotransfer function (continuous parametric PTF and point PTF).

No description available.

Heavy oil production depends on the understanding of mechanical and flow properties of unconsolidated or weakly consolidated sands under different loading paths and boundary conditions. Reconstituted bitumen-free Athabasca oil-sands samples were used to investigate the geomechanics of a steam injection process such as the Steam Assisted Gravity Drainage (SAGD). Four stress paths have been studied in this work: triaxial compression, radial extension, pore pressure increase and isotropic compression. Absolute permeability, end-point relative permeability to oil & water (kro and krw), initial water saturation and residual oil saturation were measured while the samples deformed. Triaxial compression is a stress path of increasing mean stress while radial extension and pore pressure increase lead to decreasing mean stress. Pore pressure increase experiments were carried out for three initial states: equal axial and confining stresses, axial stress greater than confining stress and confining stress greater than axial stress. Pore pressure was increased under four boundary conditions: 1) constant axial and confining stress; 2) constant axial stress and zero radial strain; 3) zero axial strain and constant confining stress; and 4) zero axial and radial strain. These experiments were designed to mimic geologic conditions where vertical stress was either S1 or S3, the lateral boundary conditions were either zero strain or constant stress, and the vertical boundary conditions were either zero strain or constant stress. Triaxial compression caused a decrease in permeability as the sample compacted, followed by appreciable permeability enhancement during sample dilation. Radial extension led to sample dilation, shear failure and permeability increase from the beginning. The krw and kro increased by 40% and 15% post-compaction respectively for the samples corresponding to lower depths during triaxial compression. For these samples, residual oil saturation decreased by as much as 40%. For radial extension, the permeability enhancement decreased with depth and ranged from 20% to 50% while the residual oil saturation decreased by up to 55%. For both stress paths, more shear-enhanced permeability was observed for samples tested at lower pressures, implying that permeability enhancement is higher for shallower sands. The pore pressure increase experiments showed an increase of only 0-10% in absolute permeability except when the effective stress became close to zero. This could possibly have occurred due to steady state flow not being reached during absolute permeability measurement. The krw curves generally increased as the pore pressure was increased from 0 psi. The increase ranged from 5% to 44% for the different boundary conditions and differential stresses. The kro curves also showed an increasing trend for most of the cases. The residual oil saturation decreased by 40-60% for samples corresponding to shallow depths while it increased by 0-10% for samples corresponding to greater depths. The reservoirs with high differential stress are more conducive to favorable changes in permeability and residual oil saturation. These results suggested that a decreasing mean stress path is more beneficial for production increase than an increasing mean stress path. The unconsolidated sands are over-consolidated because of previous ice loading which makes the sand matrix stiffer. In this work, it was found that over-consolidation, as expected, decreased the porosity and permeability (40-50%) and increased the Young’s and bulk moduli of the sand. The result is sand which failed at higher than expected stress during triaxial compression. Overall, results show that lab experiments support increased permeability due to steam injection operations in heavy oil, and more importantly, the observed reduction in residual oil saturation implies SAGD induced deformation should improve recovery factors. / text