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Cope-type Hydroamination of Alkenes with Hydroxylamines and Hydrazines - Scope and MechanismLoiseau, Francis 14 February 2013 (has links)
Hydroamination stands as a desirable approach to nitrogen-containing molecules, which have important applications ranging from pharmaceuticals (fine chemicals) to paints, coatings, insecticides and agrochemicals (bulk chemicals). It features the use of alkene and alkyne starting materials, which are abundant and rarely used in the formation of C-N bonds. This work aims at building on the improved Cope-type reactivity developed in the Beauchemin group by expanding the reach of the reaction and understanding its mechanistic complexities. The first part of this thesis describes the development of cascade reactions to provide a thermodynamic driving force for the intermolecular Cope-type hydroamination of alkenes. The methodology serves as a proof of concept that the dipolar reaction intermediates can be engineered to further react irreversibly to more stable products, and has shown potential in improving the syntheses of natural alkaloids. The second part of the thesis describes the expansion of Cope-type hydrazide hydroaminations through a systematic investigation of hydrazine analogs as reactants. Optimized reagents are featured in the first reported intermolecular Cope-type hydrohydrazidation of alkenes. Mechanistic investigations and isolation of ammonium ylide intermediates support a 5-membered concerted and planar mechanistic pathway for hydrazide hydroaminations, similar to that observed with hydroxylamines. The final section presents mechanistic data disproving a previously assumed difficult proton transfer step in the hydroamination using hydroxylamines. From such findings, early results are presented towards a hydrogen-bond catalyzed hydroamination, which has potential applicability across the field of Cope-type hydroaminations and beyond.
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Tunneling in hydrogen atom transfer reactions of ruthenium complexes, nitroxyl radicals, and hydroxylamines /Wu, Adam Cheng-Hong, January 2008 (has links)
Thesis (Ph. D.)--University of Washington, 2008. / Vita. Includes bibliographical references (leaves 136-149).
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Cope-type Hydroamination of Alkenes with Hydroxylamines and Hydrazines - Scope and MechanismLoiseau, Francis January 2013 (has links)
Hydroamination stands as a desirable approach to nitrogen-containing molecules, which have important applications ranging from pharmaceuticals (fine chemicals) to paints, coatings, insecticides and agrochemicals (bulk chemicals). It features the use of alkene and alkyne starting materials, which are abundant and rarely used in the formation of C-N bonds. This work aims at building on the improved Cope-type reactivity developed in the Beauchemin group by expanding the reach of the reaction and understanding its mechanistic complexities. The first part of this thesis describes the development of cascade reactions to provide a thermodynamic driving force for the intermolecular Cope-type hydroamination of alkenes. The methodology serves as a proof of concept that the dipolar reaction intermediates can be engineered to further react irreversibly to more stable products, and has shown potential in improving the syntheses of natural alkaloids. The second part of the thesis describes the expansion of Cope-type hydrazide hydroaminations through a systematic investigation of hydrazine analogs as reactants. Optimized reagents are featured in the first reported intermolecular Cope-type hydrohydrazidation of alkenes. Mechanistic investigations and isolation of ammonium ylide intermediates support a 5-membered concerted and planar mechanistic pathway for hydrazide hydroaminations, similar to that observed with hydroxylamines. The final section presents mechanistic data disproving a previously assumed difficult proton transfer step in the hydroamination using hydroxylamines. From such findings, early results are presented towards a hydrogen-bond catalyzed hydroamination, which has potential applicability across the field of Cope-type hydroaminations and beyond.
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Optimisation of selective extraction techniques as a tool for geochemical mapping in the Southern Africa regionAkinyemi, Segun Ajayi January 2008 (has links)
Magister Scientiae - MSc / The complex nature and composition of regolith cover in Southern Africa is a major challenge to geochemical mapping for concealed mineralization. Some of the setbacks to successful geochemical exploration may be ascribed to the use of various partial extraction techniques,without a profound understanding of the regolith components and their composition. This investigation therefore focuses on the use of hydroxylamine partial extraction geochemistry for geochemical mapping in regolith over two contrasting environments viz; aeolian sand-calcrete regolith over Au mineralization at Amalia Blue Dot Mine in South Africa and lateritic regolith covering the Ni-Cu deposit at Kabanga Main and Luhuma in Tanzania. Regolith samples from the above areas were sieved and extracted with hydroxylamine hydrochloride solution and analyzed for multi-element by AAS and ICP-MS techniques. A stepwise optimization of the hydroxylamine extraction technique of samples from both areas was carried out and incorporated into the analytical programme (in a pilot study). Results of hydroxylamine partial extraction generally gave better anomaly contrast and reflection of bedrock mineralization than the conventional aqua regia techniques that were previously used in the region. The results however show that lateritic regolith may be best extracted using 0.25M hydroxylamine while 0.1M concentration appears most suitable for extraction of aeolian-calcrete regolith. The above results are corroborated by principal component analysis of the analytical data that show various element associations, e.g. with Fe-Mn oxides while others possibly belong to the loosely adsorbed or exchangeable group. The gochemical maps in the pilot study areas at Amalia, Kabanga and Luhuma show elevated element contents or clusters of anomalies of diverse elements associated with Fe-Mn oxides. Geochemical mapping at Kabanga with deeply concealed mineralization however shows variability of subdued element patterns over mineralized areas. Geochemical signatures associated with hydroxylamine hydrochloride partial leach are therefore characterized by a lower geochemical background than that using conventional aqua regia leach. This study leads recommending for further investigations into partial extraction of the exchangeable group of elements, possibly using ammonium acetate. / South Africa
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Rh(III)-Catalyzed Alkene Difunctionalization for the Synthesis of Nitrogen-Containing CompoundsLee, Sumin January 2021 (has links)
Nitrogen-containing compounds are essential structural units in a myriad of biologically active molecules including pharmaceuticals. Although numerous synthetic methods have been developed over the last few decades, new methods constructing them in an efficient way from readily accessible starting material are still great of interest. As a coupling partner of the reaction, alkenes are abundant, general, and therefore ideal starting materials to synthesize a variety of complex, value-added products. In this thesis, we have utilized Rh(III) catalysis to develop efficient synthetic methodologies for nitrogen-containing compounds using alkenes as coupling partners.
In Chapter 2, we developed a unique disconnection approach to pyrrolidines using a-olefins as a 4-carbon source and hydroxylamine derivatives as a nitrogen source of the reaction. In Chapter 3, regio- and diastereoselective synthesis of a,b-unsaturated-d-lactams from acrylamide and unactivated alkenes initiated from C-H activation are discussed. In Chapters 4 and 5, three-component alkene difunctionalization of alkenes delivering acyclic aminated products including a-amino acids are described.
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SURFACE SCIENCE ASPECTS OF ELECTROCATALYSISMatic, Nikola 11 June 2014 (has links)
No description available.
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Design et synthèse stéréocontrôlée d’oligoglycomimétiques de type phostone et hydroxylamine / Design and stereocontrolled synthesis of phostones and hydroxylamine-type glycomimeticsFerry, Angélique 08 November 2013 (has links)
L’importance des oligosaccharides, et plus particulièrement des β-glucanes et des mannanes, dans les processus biologiques, confère à ces familles de biomolécules des propriétés riches et variées. Celles-ci permettent d’envisager des applications potentielles dans de nombreux domaines, et notamment dans le cas de problèmes de santé publique majeurs, tels que les maladies cardiovasculaires, le cancer ou encore les infections. Néanmoins, malgré les énormes avancées faites en glycochimie, la synthèse d’oligosaccharides à longue chaîne reste un défi synthétique important. La synthèse de glycomimétiques, proches structurellement des sucres naturels et accessibles via une chimie efficace, nous a semblé judicieuse. Inspirés du design des glycomimétiques existants, nous avons élaboré la synthèse de deux mimes du centre anomérique : le premier de type phosphonate et le second de type hydroxylamine.Le lien phosphonate a été choisi car il nous permet de garder un centre stéréogène sur la position anomérique, donnant ainsi la possibilité de créer les deux configurations α et β. Ceci nécessite cependant l’élaboration d’une synthèse stéréosélective. Le lien inter-résidus a donc été construit par couplage stéréosélectif entre une espèce phosphonite-borane diastéréopure et un alcool de type phostone, suivi d’une oxydation stéréospécifique de la fonction phosphonite-borane en phosphonate. Les phosphonite-boranes ont été obtenus en cinq étapes à partir du D-glucal (Schéma 2). L’étape clé de couplage passe par un mécanisme faisant intervenir deux activations successives de la fonction phosphorée apportant la réactivité nécessaire pour une attaque de l’alcool. Des stéréosélectivités variables ont été obtenues en fonction des conditions réactionnelles et du groupement protecteur en position 2 du substrat de départ. Cependant, seuls des alcools primaires peuvent être introduits. Trois dimères phostone-phostone possédant un lien (1→6) ont ainsi été obtenus. Le choix du lien hydroxylamine a été motivé par le fait que la barrière d’inversion de l’azote dans ce type de fonction est faible, ce qui implique que l’atome d’azote n’est pas stéréogène. Cette particularité permet d’éviter une synthèse stéréosélective du centre anomérique. De plus, les hydroxylamines étant peu basiques, elles ne seront pas protonées en milieu physiologique et pourraient donc être de bons mimes des glycanes naturels. Le lien inter-résidus a été construit via une double amination réductrice entre un dialdéhyde et une hydroxylamine portée par une pipéridine polyhydroxylée. Ces deux composés ont été obtenus par un processus diastéréo- et énantiosélectif à partir du cyclopentadiénylure de sodium. La combinaison de deux groupements protecteurs Boc sur l’hydroxylamine s’est révélée être la plus adéquate pour le bon déroulement de l’étape clé de double amination réductrice. Cette séquence implique deux étapes « one-pot » consistant en la formation d’une dioxime, qui subit dans un second temps une réduction, pour former l’hétérocycle. Ce processus de création du lien inter-résidus a pu être réitéré avec succès pour la synthèse d’un dimère / The importance of oligosaccharides in biological processes and particularly β-glucanes and mannanes, gives to these families of biomolecules numerous properties. These natural polymers may find potential applications in many areas, particularly in the case of major public health problems such as cardiovascular disease, cancer or infections.Despite many advances in this field, many challenges remain particularly pertaining to the assembly of higher oligosaccharides. The synthesis of glycomimetics, structurally close to natural sugars and accessible via an efficient chemistry could be an alternative. Inspired by the known glycomimetics, we have elaborated the synthesis of two new mimetics of the anomeric center: cyclic phosphonate (phostone) and hydroxylamine. The phosphonate linkage was chosen because it contains a stereogenic center on the anomeric position, with the possibility to create the two configurations α and β via a stereoselective synthesis. The linkage was built by a stereoselective coupling step between a diastereopure phosphonite-borane and a phostone-type alcohol, followed by a stereospecific oxidation of the phosphonite-borane function into phosphonate. The phosphonite-boranes were obtained in five steps from D-glucal (Scheme 2). The mechanism of the key coupling step involves two successive activations of the phosphorus function for the alcohol attack. Different stereoselectivities were obtained depending on the reaction conditions and the protecting group on the position 2. However, only primary alcohols can be introduced. Three phostone-phostone dimers possessing a (1→6) linkage were synthesized.The choice of the hydroxylamino linkage was motivated by the fact that the nitrogen barrier of inversion in this type of function is low, which means that the nitrogen is not stereogenic. This characteristic avoids a stereoselective synthesis of the anomeric center. Moreover, hydroxylamines being weakly basic, they won’t be protonated in physiological conditions and could be good mimetics of natural glycans. The linkage was built via a double reductive amination between a dialdehyde and a hydroxylamine carried by a polyhydroxylated piperidine. These two compounds were obtained by a diastereo- and enantioselective process from sodium cyclopentadienylide. The combinaison of two Boc protecting groups on the hydroxylamine proved to be the most appropriate for the key double reductive amination. This process consists in a « one-pot » two-steps sequence consisting in the formation of a dioxime, followed by its reduction to form the heterocycle. This process could be successfully reiterated for dimer and trimer synthesis
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Intramolecular Cope-Type Hydroamination of Alkenes in the Synthesis of Alkaloids: Total Synthesis of (±)-Coniine and (±)-Desbromoarborescidine A and Studies on a Novel Amination Strategy Towards Manzamine ADion, Isabelle 16 July 2012 (has links)
Intramolecular hydroamination represents a potentially general, simple strategy to access various nitrogen heterocycles. While important progress has been accomplished in recent years, six-membered ring formation via alkene hydroamination is typically difficult and limited to terminal alkenes, suggesting that only 2-methylpiperidines can be accessed reliably with current methods. As part of the Beauchemin group efforts on metal-free concerted hydroamination methods, the first part of this thesis describes the development of a Cope-type hydroamination-Meisenheimer rearrangement (CHMR) sequence that is applicable in inter- and intramolecular reactions. Data acquired from optimization on a difficult substrate (coniine) and the successful application of the CHMR sequence to the syntheses of N-norreticuline and 10-desbromoarborescidine are reported. The amination of alkenes is surprisingly scarcely used in the synthesis of complex alkaloids despite its potential for the construction of structurally challenging molecules while avoiding functional group interconversions. Hence, the second part of this thesis describes the studies on a novel amination sequence, consisting of an intermolecular Diels-Alder followed by an intramolecular hydroamination reaction, in the efforts towards the synthesis of biologically active and structurally complex Manzamine A. As such, the synthesis of the model substrates, including the development of a novel family of aminodienes, as well as the assessment of their reactivity towards [4+2] cycloadditions is reported.
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Intramolecular Cope-Type Hydroamination of Alkenes in the Synthesis of Alkaloids: Total Synthesis of (±)-Coniine and (±)-Desbromoarborescidine A and Studies on a Novel Amination Strategy Towards Manzamine ADion, Isabelle 16 July 2012 (has links)
Intramolecular hydroamination represents a potentially general, simple strategy to access various nitrogen heterocycles. While important progress has been accomplished in recent years, six-membered ring formation via alkene hydroamination is typically difficult and limited to terminal alkenes, suggesting that only 2-methylpiperidines can be accessed reliably with current methods. As part of the Beauchemin group efforts on metal-free concerted hydroamination methods, the first part of this thesis describes the development of a Cope-type hydroamination-Meisenheimer rearrangement (CHMR) sequence that is applicable in inter- and intramolecular reactions. Data acquired from optimization on a difficult substrate (coniine) and the successful application of the CHMR sequence to the syntheses of N-norreticuline and 10-desbromoarborescidine are reported. The amination of alkenes is surprisingly scarcely used in the synthesis of complex alkaloids despite its potential for the construction of structurally challenging molecules while avoiding functional group interconversions. Hence, the second part of this thesis describes the studies on a novel amination sequence, consisting of an intermolecular Diels-Alder followed by an intramolecular hydroamination reaction, in the efforts towards the synthesis of biologically active and structurally complex Manzamine A. As such, the synthesis of the model substrates, including the development of a novel family of aminodienes, as well as the assessment of their reactivity towards [4+2] cycloadditions is reported.
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Signal derived from photosynthic electron transport regulates the expression of methionine sulfoxide reductase (Msr) gene in the green macroalga Ulva fasciata DelileHsu, Yuan-ting 20 November 2008 (has links)
This study has investigated the involvement of photosynthetic electron transport chain on the regulation of gene expression of methionine sulfoxide reductase (UfMSR) in the marine macroalga Ulva fasciata Delile.UfMSRA is from copper stress and UfMSRB ir from hypersalinity stress. UfMSRA is similar to Arabidopsis AtMSRA4 and UfMSRB is similar to AtMSRB1. UfMSRA is specific to the MetSO S-enantiomer and UfMSRB catalytically reduces the MetSO R-enantiomer. Both enzymes are required, since in the cell oxidation of Met residues at the sulfur atom results in a racemic mixture of the two stereoisomers. UfMSRA and UfMSRB transcripts were increased by white light, blue light and red light with the maximum at 1 h following a decline, but kept constant in the dark. The magnitude of UfMSRA and UfMSRB transcript increase showed a positive linear correlation to increasing light intensity from 0-1200 u mole¡Pm-2¡Ps-1. The treatment with linear electron transport
chain inhibitors, hydroxylamine, 3-(3,4-dichlorophenyl) -1,1-dimethylurea (DCMU),
2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone (DBMIB) and stigmatellin,
effectively inhibited PS II activity under 300 u mole¡Pm-2¡Ps-1 irradiance. DBMIB and
stigmatellin can increase UfMSRA transcript that was reversed by
2,6-dichlorophenolindophenol (DCPIP), a PS I electron donor. It indicates that the
block of electron transport of the downstream of cytochrome b6f indeuces UfMSRA
gene expression. Hydroxylamine, DCMU and DBMIB decreased UfMSRB transcript
that was not reversed by DCPIP while stigmatellin increased UfMSRB mRNA level,
reflecting a role of reduced state with Qo site located at cytochrome b6f on the
induction of UfMSRB gene expression. The cyclic electron transport chain inhibitors,
antimycin A that inhibited photosynthetic electron transport, can inhibit the increase
of UfMSRA and UfMSRB transcripts by irradiance. UfMSRA and UfMSRB gene
expression were both modulated by cyclic electron transport chain and linear electron
transport chain. These results reveal that photosynthetic electron transport chain
modulates UfMSRA and UfMSRB gene expression by change its redox state.
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