Dans ces travaux de thèse, nous proposons de nouvelles méthodes d’estimation de canal pour un système full-duplex dédié aux communications véhiculaires. Les deux canaux relatifs au signal utile (SOI) et au signal interférant (SI) sont estimés. Les méthodes que nous proposons sont classées selon si les pilotes des deux signaux sont envoyés séparément ou simultanément. Dans le cas de la transmission séparée des pilotes, nous proposons un algorithme se basant sur un positionnement dynamique des pilotes ainsi qu’une méthode hybride qui combine l’approche du changement de position des pilotes avec l’emploi des séquences d’apprentissage en début de trame. Nous proposons également une méthode visant à optimiser l’estimation classique qui se base sur un séquence d’apprentissage en amélioration l’estimation au niveau de chaque symbole préambule. Dans le contexte d’une transmission simultanée des pilotes, nous proposons deux algorithmes visant à améliorer les performances d’estimation par rapport aux méthodes existantes. Dans la première méthode proposée, les deux canaux SI et SOI sont estimés dans le domaine fréquentiel à l’aide des itérations de Landweber. La seconde proposition consiste à utiliser une matrice de projectionafin d’éviter le bruit engendré par les données inconnues du signal SOI lors de l’estimation. Finalement, nous proposons une méthode d’estimation de canal sélectif en temps et en fréquence pour des fréquences doppler faibles à modérées. Certaines méthodes proposées sont implémentées dans un système full-duplex expérimental qui a recours aux antennes reconfigurables pour réaliser l’annulation passive. / In this work of thesis, we propose new channel estimation approaches for a full-duplex system dédicated to vehicular communications. Both the self-interference (SI) and intended (SOI) channel are estimated. We propose different estimation méthods according to whether the pilots of the signals are transmitted jointly or separately. In the separate transmission, an estimation based on a new pilot configuration is proposed as well as a hybrid method which use both pilot configuration and training sequences.We also propose an optimisation of the conventional training-based method.It consists of improving the estimation of each training symbole. In the joint transmission, we propose two algorithms that aims to improve the estimation performances compared to the existing methods. In the first proposed method, the two channels are first estimated in the frequency domain using the Landweber iterations. The second proposition consists of using a projection matrix to manipulate only the pilots and avoid the noise that is caused by the SOI unknown datas. Finally, we propose a time and frequency-selective channel estimation for low and medium doppler frequency. Some of the proposed estimators are implemented on a real Full Duplex communication system which use Multi-reconfigurable antennas to perform the passive cancellation.

Au cours des vingt dernières années, le débit croissant des communications radiofréquences a imposé la mise en œuvre de techniques d'égalisation de plus en plus complexes. Pour résoudre ce problème, les modulations multi-porteuses ont été massivement employées dans les standards de communications à très haut débit. Un exemple caractéristique de la démocratisation de ces formes d'ondes est l'utilisation de l'OFDM (Orthogonal Frequency Division Multiplexing) sur le lien descendant des réseaux 4G. Toutefois, pour les futurs réseaux 5G, l'émergence prévue des communications M2M (Machine-to-Machine) impose aux formes d'ondes une grande tolérance aux asynchronismes au sein de ces réseaux et ne permet pas l'emploi de l'OFDM qui nécessite une synchronisation stricte en temps et en fréquence. Egalement, l'utilisation efficace du spectre par les techniques de la radio cognitive est incompatible avec l'OFDM en raison de la mauvaise localisation en fréquence de cette forme d'onde.Dans ce contexte, la forme d'onde FBMC-OQAM (Filter Bank Multi-Carrier - Offset Quadrature Amplitude Modulation) est apparue comme une solution potentielle à ces problèmes. Toutefois, l'égalisation des signaux FBMC-OQAM en canal sélectif en fréquence et/ou canal MIMO (Multiple Input Multiple Output) est rendue difficile par la subsistance d'interférences entre les sous-porteuses du schéma FBMC-OQAM. Cette thèse étudie donc l'égalisation de ces liaisons. L'étude de récepteurs WL (Widely Linear) qui permettent la suppression d'interférences, sans diversité d'antenne en réception, au sein des réseaux utilisant des signaux noncirculaires au second ordre (e.g. signaux ASK, GMSK, OQAM) est privilégiée. Cette technique nommée SAIC (Single Antenna Interference Cancellation) et utilisée dans les réseaux GSM pour la suppression d'interférences co-canal est envisagée pour une extension à la suppression des interférences entre porteuses des formes d'ondes FBMC-OQAM. La technologie SAIC, qui a été étendue pour plusieurs antennes en réception (MAIC - Multiple Antenna Interference Cancellation) a l'avantage de sa faible complexité et ne génère pas de propagation d'erreur à faible SNR contrairement aux solutions de suppression successive d'interférences. Une approche progressive est adoptée, depuis l'élaboration du SAIC pour la suppression d'interférences co-canal où nous démontrons l'importance de considérer le caractère cyclostationnaire des signaux OQAM. Basée sur cette constatation, une nouvelle structure de réception utilisant un filtre WL-FRESH (FREquency-SHift) est proposée et ses meilleures performances comparé au récepteur WL standard sont présentées analytiquement et par simulations numériques. L'extension du SAIC pour la suppression d'une interférence décalée en fréquence est ensuite menée et différentes structures de réception sont proposées et analysées en détail. L'aptitude des traitements SAIC utilisant des filtres WL-FRESH à supprimer 2 interférences décalées en fréquence est présentée. Dans le contexte des signaux FBMC-OQAM qui utilisent généralement le filtre de mise en forme PHYDYAS, chaque sous-porteuse est polluée par ses deux sous-porteuses adjacentes. Cependant, pour évaluer les traitements SAIC sans devoir prendre en compte la contribution des sous-porteuses voisines à ces sous-porteuses adjacentes, un filtre doit précéder le traitement de réception. Pour cette raison, l'analyse de l'impact d'un filtre de réception sur les performances des traitements SAIC proposés est effectuée et les conditions sur la bande passante du filtre nécessaires pour justifier l'intérêt d'un traitement SAIC par filtrage WL sont présentées. Dans un dernier temps, une approche alternative d'égalisation des signaux FBMC-OQAM est présentée. Elle consiste à démoduler conjointement les sous-porteuses interférentes après filtrage. Cette technique est abordée dans le contexte de liaisons MIMO Alamouti FBMC-OQAM. / During the last two decades, the increase of wireless communications throughput has necessitated more and more complex equalization techniques. To solve this issue, multicarrier modulations have been massively adopted in high data rates wireless communications standards. A typical example of the wide use of these waveforms is the adoption of OFDM (Orthogonal Frequency Division Multiplexing) for the downlink of 4G mobile networks. However, for next-generation 5G networks, the expected increase of M2M (Machine-to-Machine) communications forbids the use of OFDM because of the tight time and frequency synchronization constraints imposed by this waveform. Additionally, efficient spectrum occupation through cognitive radio strategies are incompatible with the poor spectral localization of OFDM. In this context, FBMC-OQAM (Filter Bank Multi-Carrier - Offset Quadrature Amplitude Modulation) waveforms appeared as a potential solution to these issues. However, equalization of FBMC-OQAM in frequency selective channels and/or MIMO (Multiple Input Multiple Output) channels is not straightforward because of residual intrinsic interferences between FBMC-OQAM subcarriers. Thus, this thesis considers equalization techniques for these links. In particular, the study of WL (Widely Linear) receivers allowing the mitigation of interferences, with only a single antenna, among networks using second-order noncircular waveforms (e.g. ASK, GMSK, OQAM signals) is privileged. This work studied this technique, named SAIC (Single Antenna Interference Cancellation) and applied for the suppression of co-channel interferences in GSM networks in order to adapt it for the cancellation of FBMC-OQAM intercarrier interferences. SAIC, which was further extended to multiple receive antennas (MAIC - Multiple Antenna Interference Cancellation) benefits from its low complexity and does not generate error propagation at low SNR contrary to successive interference cancellation based solutions. A progressive approach is adopted, from SAIC/MAIC for the suppression of co-channel interferences where we emphasize the importance of considering the cyclostationary nature of OQAM communication signals. Based on this, the proposal of a new WL-FRESH (FREquency-SHift) filter based receiver for OQAM-like signals is made and its performance is characterized analytically and by numerical simulations asserting its superior performance with respect to the standard WL receiver. The extension of SAIC/MAIC for the mitigation of a frequency-shifted interference is then considered and reception structures are proposed and analyzed in detail. The ability of WL-FRESH filter based SAIC receivers to perform the suppression of multiple frequency-shifted interferences is assessed. In the context of FBMC-OQAM signals which frequently utilize the PHYDYAS pulse-shaping prototype filter, each subcarrier is polluted only by its adjacent subcarriers. However, to evaluate SAIC processing without having to consider neighboring subcarriers of the adjacent ones, a filtering operation prior to the SAIC processing is needed. For this reason, the impact of a reception filter on the performance gain provided by the SAIC processing was conducted and conditions on the filter bandwidth have been established which governs the potential performance gain of a WL filter based processing for SAIC of frequency-shifted interferences.In a last step, an alternative equalization approach for FBMC-OQAM is investigated. This proposed technique consists in the per-subcarrier joint demodulation of the subcarrier of interest and its interfering adjacent ones after a filtering step. This proposal is considered in the context of MIMO Alamouti FBMC-OQAM links.

This dissertation describes the synthesis, antimicrobial properties, and catalytic activity of a variety of eta5-ligand rhodium and iridium complexes. Cp*RM(beta-diketonato)Cl (Cp*R = R-substituted tetramethylcyclopentadienyl ligand) complexes were found to have selective activity against Mycobacterium smegmatis, with activity highly dependent upon the substituents on the Cp*R ligand as well as on the beta-diketonato ligand. These complexes were synthesized in good yield from the reaction of the chloro bridged dimers ([Cp*RMCl2]2) with the desired beta-diketonato ligand under basic conditions. All complexes were fully characterized by 1H and 13C NMR. Twenty single crystal X-ray structures were solved. The success of these syntheses led to investigation of another beta-diketonato ligand: 1,1,1,5,5,5-hexafluoroacetylacetonate (hfac). Though many metal complexes of this ligand are known, reaction with [Cp*MCl2]2 did not yield the desired Cp*M(hfac)Cl complexes. Instead, a variety of products were obtained, three of which were characterized crystallographically. The most interesting structure featured a non-coordinating trifluoroacetate (TFA) anion and a [Cp*Ir]3Na1O4 cubane structure, which is an unprecedented and highly unusual arrangement for iridium. Attempts to synthesize this cluster rationally through reactions of [Cp*IrCl2]2 with TFA yielded instead a chloro bridged [Cp*IrCl(TFA)] dimer. Reaction of [Cp*MCl2]2 with 1,1,1-trifluoroacetylacetonate (tfac) yielded the expected Cp*M(tfac)Cl complex, indicating that the problem lies with using hfac as a ligand for Cp*M(III) complexes. Finally, the indenyl effect was investigated for the oxidative annulation of 2-phenylimidazole with 1-phenyl-1-propyne catalyzed by a series of methyl-substituted [(indenyl)RhCl2] dimers. [(Ind*)RhCl2]2 was found to have significantly greater activity than [Cp*RhCl2]2 (100% vs. 51%). Two plausible catalytic cycles were proposed, one of which invokes a ring slip transition state. Though it is unclear if the "indenyl effect" is responsible for this differing activity, it is certainly apparent that using an indenyl ligand has a notable effect in this catalytic reaction. Cyclometalation was also investigated stoichiometrically for 2-phenyl-1H-imidazole and 1-phenylpyrazole and found to proceed readily for [(Ind*)RhCl2]2. Additionally, the crystallographic structure of a Rh+ /Rh– ionic pair was solved. Ionic pairs such as this are rarely found in the literature. / Doctor of Philosophy / This dissertation deals with the uses of a series of unusual compounds containing the metals rhodium and iridium. Though these are rare and expensive metals, the uses and benefits described in this dissertation far outweigh the costs. Overall, the compounds described in this dissertation are colorfully characterized as “piano stool” compounds because of their overall shape and appearance. The metal, either rhodium or iridium, occupies a central point in the complex. On top of the metal is a “flat” organic group that gives the appearance of the seat of the piano stool. Below the metal, there are three other groups that look like the legs of the piano stool. By appropriate choice of the metals and the surrounding groups, special properties can be designed into these “piano stool” complexes. Chapter 2 describes the synthesis of a series of complexes where the “flat” group is a variant of a five-membered carbon ring compound known as cyclopentadienyl, the metal is rhodium or iridium, and two of the three legs come from a family of compounds known as acetylacetonates (acac). This series of piano stool compounds display antimicrobial activity against a class of pathogens known as mycobacteria, an example of which causes the disease tuberculosis. Changing the cyclopentadienyl group and the acac group allows for this antimicrobial activity to be tuned. In the following chapter, attempts to make the same type of compound described in the paragraph above with fluorine-substituted acacs gave some very unexpected results. The most surprising result was a very unusual cube-shaped structure containing 3 iridium atoms, 1 sodium atom, and 4 oxygen atoms, which is an unprecedented arrangement for iridium. Finally, there is a specific example of a flat group for the piano stool known as indenyl. Indenyl is intriguing because it can change shape from a flat group to a bent group. In doing this, it provides more space around the metal for other molecules to bind. The result of this work shows that piano stool compounds created with this indenyl group are more active and selective for carrying out a catalytic reaction to make new ring systems that could have potential use in the synthesis of new flavorings, fragrances, and even pharmaceuticals.

Les technologies de la reconnaissance de la parole ont des performances acceptables si l'on utilise un micro dans des environnements calmes. Si des micros se situent à une position distante d'un locuteur, il faut développer des techniques de la soustraction de bruits et de réverbération. Une technique pour réduire des sons émis par les appareils environnants est proposée. Bien que l'annulation adaptative du bruit (ANC) soit une solution possible, l'excès de soustraction peut causer la distorsion de la parole estimée. Le système proposé utilise la structure harmonique des segments vocaliques que les ANCs conventionnels n'a pas prise en compte directement. La méthode de déréverbération conventionnelle provoque l'excès de soustraction car on suppose que la caractéristique de fréquence, est plate. Il faut donc estimer le temps réel de réverbération pour résoudre ce problème. On propose une méthode de déréverbération aveugle utilisant un micro avec des fonctions d'autocorrélation sur la séquence de composants à chaque fréquence. Une technique pour échapper au problème de permutation qui se provoque lorsqu'on utilise l'analyse en composantes indépendantes (ICA) dans le domaine de fréquence, est également proposée : le Multi-bin ICA. Enfin, ce travail propose une technique pour estimer les spectres de bruit et de parole sans développer de modèle de gaussienne à mélange (GMM). Le spectre de la parole est modélisé à l'aide mélange de processus de Dirichlet (Dirichlet Process Mixture : ‘DPM') au lieu du GMM.

Duas abordagens foram estudadas para a síntese enantiosseletiva do (+)-4a-H-eudesman-5a-ol ou (+)-pendulol (128) (esquema 1) . Numa primeira rota sintética (Rota 1), construiu-se enantiosseletivamente a octalona 92 , por urna reação de anelação de Robinson assimétrica via imina quiral. A redução da octalona 92, produziu o f3-álcool 114, que por desoxigenação do carbono C-3, forneceu a octalina 120. Contando com a possibilidade da metila angular induzir estereosseletividade na epoxidação da ligação dupla endocíc1ica na octalina 120, tentou-se a obtenção do a-epóxido 124. Entretanto, este foi obtido em urna mistura equimolecular com seu diastereoisômero, o f3-epóxido 124a. Numa segunda alternativa sintética (Rota 2), foi estudada a redução da octalona 92 L-selectride® de modo a obter-se o a-álcool 115. A complexação da a-hidroxila do substrato com o agente epoxidante, com posterior desoxigenação do carbono C-3, poderia permitir a preparação estereosseletiva do epóxido 124. O resultado desta etapa de redução não forneceu o produto esperado em rendimento apreciável, o que conduziu à utilização da metodologia de inversão da configuração da hidroxila em 114, desenvolvida por Mitsunobu. O a-álcool 115 foi obtido e epoxidado fornecendo o epoxi-álcool135. As tentativas de desoxigenação do carbono C-3via xantato não forneceram o a-epóxido 124. Desta forma optou-se pela abertura do anel oxirano em 135, sendo obtido o dio1137. Este foi submetido à mesilaçãoda hidroxila em C-3 com posterior redução por LiAIH4, o que forneceu urna mistura de prováveis produtos de eliminação, não permitindo a obtenção do (+)-pendulol (128). esquema 1: rotas sintéticas para a sintese enatiosseletiva do (+)-pendulol. / Two approaches were studied to the enantioselective synthesis of (+)-4a-H-eudesman-Sa-ol or (+)-pendulol (128) (scheme 1). On a first synthetic route (route 1), the octalone 92 was prepared by a Robinson annulation reaction via chiral imine. The reduction of compound 92 and deoxigenation on the C-3 carbon of the correspondent p-alcohol 114, led to the octalin 120. We expect that the angular methyl grou p could exerce sterical hindrance on the p-face of the biciclic sistem and thus directec de epoxidation to the opposite side to afford the epoxide 124 estereosselectively. However, the desired epoxide 124 was obtained in an equimolecular mixture with the diastereoisomer 124a. On a second alternative synthetic route (route 2), was studied reduction of octalone 92 L-selectride® to afford the a-alcohol 115. The expected complexation of the a-hidroxyl group to the epoxidizing agent could permit the stereoselective preparation of epoxide 124. the result of this step doens't led to the expected product in good yield. 80 one alternative was the invertion of the hidroxyl configuration on carbon C-3 in compound 114, via Mitsunobu methodology. The a-alcohol 115 was obtained and epoxidized to afford the epoxi-alcohol 135. All affords to deoxigenate the C-3 carbon via xantate do not permit the preparation of the epoxide 124. 80, the oppenning of the oxirane ring in compound 135 was done first, ledding to the diol 137. This compound was submitted to mesylation folowed by reduction, ledding to a mixture of probable elimination products, but de (+)-pendulol (128) was not detected. scheme 1: synthetic routes to the enantioselective synthesis of (+)-pendulol.

Cette thèse propose un nouveau processus de réservation d'examens IRM (Imagerie par Résonance Magnétique) afin de réduire les temps d’attente d’examens d'imagerie des patients atteint d'un AVC (Accident Vasculaire Cérébral) soignés dans une unité neurovasculaire. Le service d’imagerie réserve chaque semaine pour l'unité neurovasculaire un nombre donné de créneaux d'examens IRM appelés CTS afin d’assurer un diagnostic rapide aux patients. L'unité neurovasculaire garde la possibilité de réservations régulières appelées RTS pour pallier les variations des flux de patients.Nous donnons d'abord une formulation mathématique du problème d'optimisation pour déterminer le nombre et la répartition des créneaux CTS appelée contrat et une politique d'affectation des patients entre les créneaux CTS ou les réservations RTS. L'objectif est de trouver le meilleur compromis entre le délai d'examens et le nombre de créneaux CTS non utilisés. Pour un contrat donné, nous avons mis en évidence les propriétés et la forme des politiques d'affectation optimales à l'aide d'une approche de processus de décision markovien à coût moyen et coût actualisé. Le contrat est ensuite déterminé par une approche d'approximation Monté Carlo et amélioré par des recherches locales. Les expérimentations numériques montrent que la nouvelle méthode de réservation permet de réduire de manière importante les délais d'examens au prix des créneaux inutilisés.Afin de réduire le nombre de CTS inutilisé, nous explorons ensuite la possibilité d’annuler des créneaux CTS un ou deux jours en avance. Une approche de processus de décision markovien est de nouveau utilisée pour prouver les propriétés et la forme de la politique optimale d’annulation. Les expérimentations numériques montrent que l'annulation avancée des créneaux CTS permet de réduire de manière importante les créneaux CTS inutilisés avec une augmentation légère des délais d'attente. / This research is motivated by our collaborations with a large French university teaching hospital in order to reduce the Length of Stay (LoS) of stroke patients treated in the neurovascular department. Quick diagnosis is critical for stroke patients but relies on expensive and heavily used imaging facilities such as MRI (Magnetic Resonance Imaging) scanners. Therefore, it is very important for the neurovascular department to reduce the patient LoS by reducing their waiting time of imaging examinations. From the neurovascular department perspective, this thesis proposes a new MRI examinations reservation process in order to reduce patient waiting times without degrading the utilization of MRI. The service provider, i.e., the imaging department, reserves each week a certain number of appropriately distributed contracted time slots (CTS) for the neurovascular department to ensure quick MRI examination of stroke patients. In addition to CTS, it is still possible for stroke patients to get MRI time slots through regular reservation (RTS). This thesis first proposes a stochastic programming model to simultaneously determine the contract decision, i.e., the number of CTS and its distribution, and the patient assignment policy to assign patients to either CTS or RTS. To solve this problem, structure properties of the optimal patient assignment policy for a given contract are proved by an average cost Markov decision process (MDP) approach. The contract is determined by a Monte Carlo approximation approach and then improved by local search. Computational experiments show that the proposed algorithms can efficiently solve the model. The new reservation process greatly reduces the average waiting time of stroke patients. At the same time, some CTS cannot be used for the lack of patients.To reduce the unused CTS, we further explore the possibility of the advance cancellation of CTS. Structure properties of optimal control policies for one-day and two-day advance cancellation are established separately via an average-cost MDP approach with appropriate modeling and advanced convexity concepts used in control of queueing systems. Computational experiments show that appropriate advance cancellations of CTS greatly reduce the unused CTS with nearly the same waiting times.

<p>In medicinal chemistry, there is a constant need for new preparative methods, both to make the synthesis process more effective, and to increase the accessibility to a wide variety of compounds. A number of different approaches can be used to attain these goals. Transition metal catalysis is generally performed under mild conditions, providing both regio- and chemoselective reactions. Thus, it offers an attractive means of preparation of complex drug candidates. Two additional methodologies used to increase the preparative efficiency are one-pot protocols and controlled microwave heating. One-pot and multi-component reactions are less time consuming than step-by-step reactions, and microwave heating has been used to considerably shorten the reaction times. </p><p>This thesis describes a new palladium-catalyzed, one-pot reaction producing racemic acetal-protected 3-hydroxy-1-indanones from ethylene glycol vinyl ether and triflates of salicylic aldehydes. The triflates were prepared using controlled microwave heating. The reaction sequence starts with a regioselective internal Heck coupling, followed by an annulation cascade. By including secondary amines in the reaction mixture, the reaction was further developed into a three-component reaction delivering racemic acetal-protected 3-amino-1-indanones. This new method was utilized for the synthesis of primary, secondary and tertiary aminoindanones. Finally, by using enantiopure t-butyl sulfinyl imines, derived from salicylic aldehyde triflates and ethylene glycol vinyl ether as starting materials in a closely related type of palladium coupling–annulation sequence, a stereoselective protocol providing enantiomerically pure 3-amino-1-indanones was developed. To demonstrate an application in medicinal chemistry, the enantiopure 3-amino-1-indanones were incorporated as P2 and/or P2´ substituents into active HIV-1 protease inhibitors.</p>

In medicinal chemistry, there is a constant need for new preparative methods, both to make the synthesis process more effective, and to increase the accessibility to a wide variety of compounds. A number of different approaches can be used to attain these goals. Transition metal catalysis is generally performed under mild conditions, providing both regio- and chemoselective reactions. Thus, it offers an attractive means of preparation of complex drug candidates. Two additional methodologies used to increase the preparative efficiency are one-pot protocols and controlled microwave heating. One-pot and multi-component reactions are less time consuming than step-by-step reactions, and microwave heating has been used to considerably shorten the reaction times. This thesis describes a new palladium-catalyzed, one-pot reaction producing racemic acetal-protected 3-hydroxy-1-indanones from ethylene glycol vinyl ether and triflates of salicylic aldehydes. The triflates were prepared using controlled microwave heating. The reaction sequence starts with a regioselective internal Heck coupling, followed by an annulation cascade. By including secondary amines in the reaction mixture, the reaction was further developed into a three-component reaction delivering racemic acetal-protected 3-amino-1-indanones. This new method was utilized for the synthesis of primary, secondary and tertiary aminoindanones. Finally, by using enantiopure t-butyl sulfinyl imines, derived from salicylic aldehyde triflates and ethylene glycol vinyl ether as starting materials in a closely related type of palladium coupling–annulation sequence, a stereoselective protocol providing enantiomerically pure 3-amino-1-indanones was developed. To demonstrate an application in medicinal chemistry, the enantiopure 3-amino-1-indanones were incorporated as P2 and/or P2´ substituents into active HIV-1 protease inhibitors.

This thesis deals with the development and application of new synthetic methodology for stereo- or regioselective construction of carbon-carbon bonds in organic synthesis. The first part of this thesis describes the development of a divergent protocol for stereoselective synthesis of chiral aminodiols by employing Mukaiyama aldol additions to syn- and anti-α-amino-β-silyloxy aldehydes. The stereoselectivity of the nucleophilic attack is governed by either chelation to the α-amino moiety or by nucleophilic attack in the Felkin-Anh sense. This study is also directed towards the elucidation of the factors that dictate aldehyde π-facial selectivity in substrate-controlled nucleophilic additions to these and similar systems. In the second part, a highly stereoselective [3 + 2]-annulation reaction of N-Ts-α-amino aldehydes and 1,3-bis(silyl)propenes for stereoselective construction of densely functionalized pyrrolidines is presented. In addition, this methodology is also implemented as a keystep in a synthetic approach towards the polyhydroxylated pyrrolidine and pyrrolizidine alkaloids DGDP and (+)-alexine from a common late pyrrolidine intermediate. Finally, a divergent protocol for regioselective opening of vinyl epoxides using alkyne nucleophiles is described, in which the regioselectivity of the nucleophilic attack is controlled by the choice of reaction conditions. The regioselectivities of the SN2 and SN2’ processes are, however, significantly influenced by the nature of the alkyne substituents and the best results are obtained using ethoxyacetylene. The SN2 opening of vinyl epoxides with ethoxyacetylene as nucleophile is also shown to provide a straightforward entry to functionalized γ-butyrolactones. / QC 20100917

Texte remanié de : Dissertation : Rechts- und Staatswissenschaftliche Fakultät : Bonn, Rheinische Friedrich-Wilhelms-Universität : 2007. / Table des matières. GRCh = Grundrechtecharta. AEUV = Vertrag über die Arbeitsweise der Europäischen Union. Notes bibliogr. Bibliogr. p. [283]-301. Index.