Les travaux de recherche fondamentale présentés ici sont ancrés au cœur de la chimie organique de synthèse moderne, et plus particulièrement dans le domaine de la multi-organocatalyse énantiosélective. Dans ce manuscrit, nous avons identifié deux organocascades originales et démontré la pertinence synthétique de l'une d'elle par des applications en synthèse totale de produits naturels. L’originalité de ce travail repose sur l’utilisation d’un NHC de la classe des 1,3-imidazol-2-ylidenes comme base de Brønsted ou base de Lewis organocatalytique / The basic research work presented herein is anchored at the core of modern synthetic organic chemistry, and more specifically in the field of enantioselective multi-organocatalysis. In this manuscript, we have identified two original organocascades and demonstrated the synthetic relevance of one of these through applications in total synthesis. The originality of the work lies on the use of a 1,3-imidazol-2-ylidene NHC as an organocatalytic Brønsted or Lewis base.

M.A.

Orientador: Marcius Cesar Soares Freire / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Artes / Made available in DSpace on 2018-08-22T01:35:58Z (GMT). No. of bitstreams: 1 MartinRojo_Sara_M.pdf: 1267423 bytes, checksum: 4f139dd6a0d384ab2af2c56a24a42cc6 (MD5) Previous issue date: 2012 / Resumo: O cinema de Haneke é um cinema de hiper-realismo; de atmosfera; que fala e responde; que traz em imagens a complexidade que caracteriza nosso questionado mundo. Este trabalho tem como foco a análise da obra do diretor austríaco Michael Haneke, através de uma revisão dos recursos estéticos e manifestações discursivas mais relevantes em seus filmes, definidos como marcas autorais. Em um primeiro momento, foi necessário realizar uma contextualização da obra como parte de um momento histórico concreto, demonstrando sua total vinculação com o pensamento modernista surgido na década dos anos 1970. Posteriormente, realizou-se uma pequena revisão biográfica do autor, ressaltando sua relação direta com o universo teatral e com a proposta estético-ideológica do dramaturgo alemão Bertolt Brecht, a qual se distingue como absolutamente dominante no pensamento do diretor. E, finalmente, realizou-se uma análise detalhada dos elementos formais mais significativos presentes nesta obra como parte da intencionalidade do diretor. Os pontos centrais com os quais trabalha esta pesquisa, que por sua vez são definidos pela herança de Brecht, são: em primeiro lugar, a ativação da consciência do espectador mediante uma reflexão sobre as imagens representadas; em segundo, a mise en scène do diretor graças à qual tal ativação acontece. Espectador e cena são, portanto, os pilares deste estudo. Para conformar o corpus do presente trabalho foram selecionados os filmes de Haneke ambientados em um momento presente, contemporâneo, para após a análise dos aspetos formais encontrados, aproximar uma critica que fala diretamente sobre o nosso mundo. Os filmes escolhidos nesta pesquisa foram os seguintes: O Sétimo Continente (1989); O Vídeo de Benny (1992); 71 Fragmentos de uma Cronologia do Acaso (1994); Violência Gratuita (1997); Código Desconhecido (2000); A Professora de Piano (2001); Caché (2005) / Abstract: Haneke's cinema is a cinema of hyper-realism, atmospheric, which speaks and answers. It translates into images the complexity that characterizes our challenged world. This work focuses on analyzing the work of Austrian director Michael Haneke through a review of the most important aesthetic resources and discursive manifestations in his films, defined as copyrighted brands. Firstly, it was necessary to contextualize the work as part of a specific historical moment, demonstrating its total link with the modernist thought emerged in the mid-70s. This is followed by a short review of the author's biography, emphasizing its his direct relationship with the theatrical universe and with the aesthetic-ideological proposal by the German playwright Bertolt Brecht, which distinguishes itself as absolutely dominant in the doctrinal thinking of the director. Finally, we carried out a detailed analysis of the most significant formal elements present in this work as part of the director's intent. The main topics addressed by this research, which in turn are defined by Brecht's legacy, are: the activation of the viewer's consciousness through a reflection of the facts represented, as a first topic, which originates through the productions created by the director, as a second topic. The spectator and the scene are therefore the pillars of this research. The aim of this study is to identify some ideas about the aesthetic design emanating from this filmography, understood as a byproduct of the renewing contemporary aesthetic thought. As part of the body of this research, Haneke's films set in a present and contemporary moment were selected in order to conclude in a critique that speaks directly about our world, after having reviewed the formal aspects found. The movies chosen for this research were the following: The Seventh Continent (1989), Benny's Video (1992), 71 Fragments of a Chronology of Chance (1994), Funny Games (1997), Code Unknown (2000), The Piano Teacher (2001) and Caché (2005) / Mestrado / Multimeios / Mestra em Multimeios

De nos jours, une des stratégies majeures dans la modulation de la pharmacocinétique des composés bioactifs est leur vectorisation et l’obtention de formes prodrogues. Ce travail est centré sur la vectorisation d’antitumoraux phosphorés à l’aide de peptides favorisant le passage membranaire. Nous avons alors réalisé la conjugaison d’aminoalkyl-bisphosphonates avec des séquences peptidiques afin de modifier leur temps de rétention dans l’organisme et d’augmenter leur internalisation cellulaire. Différents espaceurs possédant un motif carbonylé insaturé ont été évalués dans le couplage par la réaction d’addition aza- et thiaMichael afin d’aboutir à l’obtention d’un conjugué peptide-alendronate. Une approche prodrogue a également été réalisée avec la synthèse de dérivés de type bisphosphinates et l’obtention d’un analogue de l’alendronate. / Nowadays, one of the main strategies for pharmacokinetic modifications of bioactive compounds is their vectorization and the synthesis of prodrug derivatives. This work is focused on the vectorization of phosphorus antitumor agents with cell-penetrating peptides. We have then conjugated aminoalkyl-bisphosphonates with peptidic sequence to modify their retention time and increase their cellular internalization. Several linkers bearing an insaturated carbonyl moiety have been evaluated in conjugation by aza- and thia-Michael addition reaction to obtain a conjugated peptide-alendronate compounds. A prodrug approach has been conducted with the synthesis of bisphosphinate derivatives and an analog of alendronate has been obtained.

Le glycérol est une molécule bio-sourcée, abondamment disponible, issue de la saponification des corps gras et de la transestérification des huiles végétales. Les travaux portent sur l'utilisation du glycérol comme base structurale de cœurs de dendrimère, en particulier par addition d'oxa-Michael sur des dérivés acryliques. La fonctionnalisation en surface de dendrimères par des motifs imidazolium est explorée afin d’obtenir un dendrimère liquide ionique (DLI) aux propriétés thermosensibles. Le chapitre bibliographique est consacré dans une première partie, aux méthodes de synthèse de dendrimère mettant en jeu des dérivés acryliques et à leurs applications et dans une seconde partie, aux travaux consacrés à l'addition oxa-Michael d'alcools sur des dérivés acryliques. Le deuxième chapitre porte sur les synthèses, à partir du glycérol, de la base structurale du cœur de dendrimère. La réaction d’acylation du glycérol par le chlorure d’acryloyle est présentée ainsi que les différentes constructions de dendrimères poly(estersulfure) à partir du triacrylate de glycérol. L’addition nucléophile du glycérol sur l’acroléine, l’acrylamide, des acrylates et l’acrylonitrile a été étudiée. Avec les acrylates, la réaction d'addition nucléophile est en compétition avec la réaction de transestérification, à l’exception de l'acrylate de t-butyle résistant en milieu basique. Avec l’acrylonitrile, la synthèse du 1,2,3-tricyanoéthylglycéryléther a pu être menée sans solvant, en 5 heures à température ambiante, en présence d’un catalyseur peu coûteux (la soude 4 mol %) avec un rendement de 88% et une pureté de 99% sans méthode de purification. Les intermédiaires de réaction mono- et di-cyanoéthylglycéryléther ont été caractérisés et ont permis un suivi cinétique de la réaction. La synthèse de dendrimères poly(amidoamine) à partir du 1,2,3-tricyanoéthylglycéryl éther fait l’objet du troisième chapitre : synthèse des générations G0 à G2,5, caractérisation des dendrimères. Des défauts de structure dus à une cyclisation intramoléculaire ont été mis en évidence par HRMS pour les générations entières et les dendrimères de demi-génération Gn+5 (n entier) sont purifiés par colonne chromatographique. Différentes voies de synthèse pour l’obtention d’un DLI à termini imidazolium sont présentées / Glycerol is a bio-based molecule, abundantly available, from the saponification of triglyceride and the transesterification of vegetable oils. The work described in this PhD thesis concerns the use of glycerol as structural base of dendrimer's core, in particular by oxa-Michael addition on acrylic derivatives. The surface functionalization of dendrimers by imidazolium units is explored in order to obtain an ionic liquid dendrimer (DLI) with thermosensitive properties. In the first part, the bibliographic chapter presents the methods of dendrimers synthesis involving acrylic derivatives and their applications and, in a second part, the work introduces the oxa-Michael addition of alcohols to acrylic derivatives. The second chapter deals with the synthesis of the structural base of the dendrimer core from glycerol. The reaction of acylation of glycerol with acryloyl chloride is presented as well as the various constructions of poly(estersulfide) dendrimers from glycerol triacrylate. The nucleophilic addition of glycerol to acrolein, acrylamide, acrylates and acrylonitrile has been studied. With the acrylates, the nucleophilic addition reaction is in competition with the transesterification reaction, with the exception of t-butyl acrylate, resistant in basic medium. With acrylonitrile, the synthesis of 1,2,3-tricyanoethylglycerylether was carried out without solvent in 5 hours at room temperature in the presence of an inexpensive catalyst (4 mol% sodium hydroxide) in a yield of 88% and purity of 99% without purification method. The mono- and di-cyanoethylglycerylether reaction intermediates were characterized and allowed kinetic monitoring of the reaction. The synthesis of poly(amidoamine) dendrimers from 1,2,3-tricyanoethylglycerylether is the subject of the third chapter: synthesis of generations G0 to G2,5 and characterization of dendrimers. The defects in the structure due to intramolecular cyclization have been demonstrated by HRMS for generations Gn and the half-generation dendrimers Gn+5 (n=0, 1, 2) were purified by chromatographic column. Several routes of synthesis for the synthesis of DLI with imidazolium termini are presented

La présence conjointe de plusieurs fonctions confère aux allylphosphonates β-éthoxycarbonylés une réactivité particulière. Ces derniers sont considérés comme d’excellents précurseurs pour l’accès à de nouveaux composés organophosphorés. Dans le présent travail, nous avons décrit, dans un premier temps, l’utilisation de ces adduits entant qu’accepteurs de Michael. En effet, nous avons effectué des additions conjuguées d ethiols, d’amines et d’anions énolates dans des conditions réactionnelles douces. Ces allylphosphonates ont été également utilisés pour la préparation d’une nouvelle famille de γ-lactames α,β-instaurés phosphono-méthylés.L’étape clé de cette synthèse est une addition conjuguée de nitroalcanes sur les allylphosphonates suivie d’une réaction de Nef..Les cétoesters ainsi obtenus sont convertis en lactames par action d’amines primaires. Des réactions d’arylations pallado-catalysées sur les allyphosphonates ont permis l’accès à des hétérocycles phosphonatés dérivant de lacoumarine, de la quinoléine et de la benzoxépinone. La synthèse de P-hétérocyclesde différentes tailles à partir des allylphosphonates a été aussi possible par la conversion du groupe phosphonate en phosphorochloridate. La réactivité de ce dernier vis-à-vis de différentes amines, a permis d’isoler une nouvelle famille de N,Phétérocyclesà 5, 7, 8 et 9 chaînons. La synthèse de P-hétérocycles à 6 chainons a été également décrite en réalisant des cyclisations dans les conditions de métathèse cyclisante (RCM) à partir d’un bisallylphosphonate et d’un bisallylphosphoramidate issus des mêmes précurseurs. / Due to the joint presence of several functional groups, β-ethoxycarbonylatedallylphosphonates are considered as excellent precursors for the preparation of neworganophosphorus compounds. In the presentwork, we first described the use of suchphosphonates as Michael acceptors. Indeed, weperformed conjugated additions of thiols,amines and enolate-anion under mild reactionconditions. Allylphosphonates were also usedfor the preparation of a new family of phosphonomethyl α,β-unsaturated γ-lactams.The key step of this sequence is a conjugateaddition of nitroalkanes on allylphosphonates followed by a Nef reaction. Ketoester intermediaites were then convertedinto lactams by reaction with primary amines.Pd-catalyzed arylations on allylphosphonates allowed preparing phosphonated heterocyclesderived from coumarin, quinolinone andbenzoxepinone skeletons. The synthesis of Pheterocyclesof various sizes fromallylphosphonates was explored by theconversion of phosphonate inphosphorochloridate. The reactivity of the latterwith amines, allowed isolation of a new familyof 5-,7-, 8- and 9-membered N,P-heterocycles.The synthesis of 6-membered P-heterocycleshas also been described by performingcyclization under the conditions of a ringclosing metathesis (RCM) starting from bisallylphosphonates and bisallylphosphoramidates.

The intent of this dissertation is to investigate Michael Tippett's eclectic approach to the sonata form in the twentieth century as demonstrated in his Sonata No. 1. Topics of discussion include historical background of English music, particularly the English piano sonata, at the turn of the century (chapter 1), biographical information and a general overview of Tippett's music (chapter 2), a brief examination of Tippett's Sonata Nos. 2, 3, and 4 (chapter 3) and a formal analysis of Sonata No. 1 as well as Tippett's approach to contrapuntal techniques, rhythm, harmony and tonality (chapter 4). In addition to the lecture recital given on February 1, 1999, three others were given: the first recital, on April 3, 1995, contained works by Beethoven, J.S. Bach/Busoni, and Bartok: the second recital, on February 5, 1996, included works by Schumann, Mozart, and Ginastera: and the third recital, on January 2, 1998, featured works by Barber and Chopin.

Philos.-Theol. Hochsch., Diss.--Benediktbeuern, 2005.

First part is focused on finding suitable reaction conditions for organocatalytic domino Michael/Michael reaction of ethyl (E)-3-(2-thiophenyl)acrylate with α,β-unsaturated aldehydes. Second part deals with the preparation of pyrazolone derivatives from commercially available compounds and describes effects of various substituents in α-position on chemical efficiency and stereoselectivity of amination with azodicarboxylate catalyzed by quinine.

Title from first page of PDF document. Includes bibliographical references (p. 20-22).