Orientador: Carlos Roque Duarte Correia / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T20:32:55Z (GMT). No. of bitstreams: 1 Lustosa_DaniloMachado_M.pdf: 59336060 bytes, checksum: e1999d97ac1f1ad2f49b0e334514c4fa (MD5) Previous issue date: 2014 / Resumo: A reação de Heck convencional consiste em uma reação entre olefinas e haletos de arila ou vinila catalisada por paládio. A variante Heck-Matsuda (HM) utiliza sais de arenodiazônio, mais reativos do que os respectivos haletos de arila ou vinila.. Por muito tempo a HM apresentava como principal limitação metodológica a ausência de uma versão enantiosseletiva. Em 2012, o grupo do prof. Carlos Correia relatou a primeira reação de Heck-Matsuda enantiosseletiva. Com o intuito de tornar esta metodologia uma ferramenta sintética mais robusta e compreender melhor esta reação, esta dissertação relata novos estudos de complexos de paládio quirais, não racêmicos, como sistemas catalíticos na arilação de 3-pirrolinas N-protegidas em reações de Heck-Matsuda enantiosseletivas. Com a utilização de complexos Pd/piridinoxazolina obteve-se adutos de Heck contendo substituintes doadores de elétrons em rendimentos de bons a excelentes e razões enantiômericas de moderadas a boas. Ao se fazer uso de sais de arenodiazônio com substituintes retiradores de elétrons, obteve-se os adutos de Heck em rendimentos de baixos a bons e razões enantiômericas de boas a excelentes. Alguns dos adutos de Heck foram selecionados e aplicados na obtenção de análogos do baclofeno e suas respectivas butirolactamas, com o objetivo de demonstrar a aplicabilidade sintética da nova metodologia e determinar a estereoquímica absoluta dos adutos de Heck obtidos (via comparação dos valores de [a]D obtidos com aqueles relatados na literatura). Por fim, com a estereoquímica dos produtos determinadas, racionalizou-se a obtenção destes adutos de forma enantiosseletiva através da apresentação de ciclos catalíticos apropriados / Abstract: The conventional Heck reaction consists of a reaction between olefins and vinyl or aryl halides catalyzed by palladium. The variant Heck-Matsuda (HM) uses arenediazonium salts, more reactive than the corresponding aryl or vinyl halides. For a long time the HM was seeing as a limited synthetic method due to the absence of its enantioselective version. In 2012, the group of prof. Carlos Correia reported the first enantioselective Heck-Matsuda reaction. Aiming at making this methodology a powerful synthetic tool, as well as to get mechanistic insights, this dissertation describes our studies on the enantioselective HM employing chiral, non-racemic, palladium complexes for the arylation of 3-N-protected- pyrrolines. With the use of Pd/pyridine-oxazoline complexes chiral Heck adducts were obtained containing electron rich substituents in good to excellent yields in enantiomeric ratios from moderate to good. When making use of arenediazonium salts with electron withdrawing substituents, the Heck adducts were obtaining in low from good yields in enantiomeric ratios from good to excellent. Some of the Heck adducts were selected in order to synthesize baclofen analogues and butyrolactams to demonstrate not only the applicability of the new method but also to determine the absolute stereochemistry of the Heck adducts (comparison of our [a]D values with those reported in the literature). Finally, with the absolute stereochemistry of the products determined, a rationale for this new enantioselective Heck-Matsuda was provided / Mestrado / Quimica Organica / Mestre em Química

Le développement d’une chimie propre et donc durable est un des challenges majeurs du 21ème siècle dans les pays industrialisés. Étant au cœur de nombreuses découvertes dans divers domaines scientifiques allant de la physique à la médecine, les sciences chimiques doivent jouer un rôle central pour résoudre un certain nombre de problèmes environnementaux auxquels nous devons faire face. Mon travail de thèse s’inscrit dans cette problématique par le développement de méthodologies de synthèse faisant intervenir plusieurs transformations dans le même réacteur. Nous avons notamment développé des séquences réactionnelles appelées HRC (pour Heck-Reduction-Cyclization, en anglais) prenant appui sur le caractère multi-tâche d’un catalyseur à base de palladium. Ces travaux nous ont permis de préparer une grande variété d’hétérocyles ou composés fonctionnalisés parmi lesquels nous pouvons citer les oxindoles, les indanones, ou encore les naphthoxindoles. Ces travaux ont donné lieu pour le moment à quatre publications dans des journaux à comité de lecture. / The development of clean chemistry and therefore sustainable is one of the major challenges of the 21st century in industrialized countries. Being in the heart of many discoveries in various scientific fields ranging from physics to medicine, the chemical sciences must play a central role in solving a number of environmental problems we face. My thesis work is part of this problem through the development of synthetic methodologies involving several transformations in the same reactor. We have developed the reaction sequences called HRC (for Heck-Reduction-cyclization) building on the multi-task of a palladium catalyst. This work allowed us to prepare a variety of functionalized heterocycles or compounds from which we can cite the oxindole, the indanones, or the naphthoxindoles. This work has resulted for the time four publications in peer-reviewed journals.