923 resultados para Friedel-Crafts intramolecular chalcones
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A criatividade tem sido mencionada desde há muito tempo pela literatura. A forma de a conceptualizar tem dependido em muito dos investigadores e da sua visão sobre o que é criatividade, porém as suas potencialidades têm tomado cada vez mais interesse pela comunidade científica. Os seus benefícios estendem-se a diversas áreas da vida humana, como sentimentos de satisfação, bem-estar e saúde mental. A investigação aqui apresentada procura encontrar modelos preditivos de comportamentos criativos, pressupondo que estes poderão ser de grande auxílio para o desenvolvimento de um melhor bem-estar psicológico. Assim a investigação comportou o uso de quatro variáveis: a pessoa, o processo, o produto e o ambiente criativo. A amostra contou com 215 estudantes universitários e os resultados revelaram o encontro de quatro modelos preditivos de comportamentos criativos, com uma maior ênfase nas artes visuais e manuais. Conclui-se com a ideia de que a predição de produtos criativos é possível e que tal poderá ser preponderante para um bom desenvolvimento da saúde mental.
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Dissertação apresentada para obtenção do grau de Mestre em Educação Social e Intervenção Comunitária
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This report presents results from a study of the creative economy associated with the arts, design, crafts and related activities in South Carolina. As this report will show, these creative individuals and enterprises exert a strong impact on the state’s economic base. Like other drivers of the regional economy, this creative activity revolves around a cluster, or a set of interrelated industries, that thrive in tandem. Along with manufacturing and agriculture, the creative cluster is a catalyst for state and local economic development. The report presents results from an analysis of the South Carolina creative cluster based on 2008 data. For the first time, this report provides a comprehensive summary of the creative economic footprint in South Carolina.
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Cette étude s’est déroulée dans le contexte de l’École en réseau au Québec. Une classe du primaire a utilisé un espace numérique collaboratif (Knowledge Forum) pour la réalisation d’activités d’éducation artistique, soit l’appréciation d’un corpus d’oeuvres et la création d’un objet d’art. La progression du discours écrit relativement à ces deux objets de partage a été étudiée. Nos résultats montrent que les élèves ont réussi à faire progresser leurs contributions sur les deux objets partagés. En interagissant entre eux, ils ont créé des artéfacts de connaissances partagées et développé un langage artistique propre. À la suite de nos constats, des implications pédagogiques ont été formulées pour d’encourager la participation des élèves lors d’activités d’éducation artistique au moyen d’outils numériques qui soutiennent la collaboration.
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A criatividade tem sido mencionada desde há muito tempo pela literatura. A forma de a conceptualizar tem dependido em muito dos investigadores e da sua visão sobre o que é criatividade, porém as suas potencialidades têm tomado cada vez mais interesse pela comunidade científica. Os seus benefícios estendem-se a diversas áreas da vida humana, como sentimentos de satisfação, bem-estar e saúde mental. A investigação aqui apresentada procura encontrar modelos preditivos de comportamentos criativos, pressupondo que estes poderão ser de grande auxílio para o desenvolvimento de um melhor bem-estar psicológico. Assim a investigação comportou o uso de quatro variáveis: a pessoa, o processo, o produto e o ambiente criativo. A amostra contou com 215 estudantes universitários e os resultados revelaram o encontro de quatro modelos preditivos de comportamentos criativos, com uma maior ênfase nas artes visuais e manuais. Conclui-se com a ideia de que a predição de produtos criativos é possível e que tal poderá ser preponderante para um bom desenvolvimento da saúde mental.
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Section 1 is focused on the bis-alkoxycarbonylation reaction of olefins, catalyzed by aryl α-diimine/Pd(II) complexes, for the synthesis of succinic acid ester derivatives, important compounds in many industrial fields. The opening chapter (Chapter 1) of this thesis presents an overview of the basic chemistry of organopalladium compounds and carbonylation reactions, focusing on oxidative bis-alkoxycarbonylation processes. In Chapter 2 the results obtained in the bis-alkoxycarbonylation of 1,2-disubstituted olefins are reported. The reaction proceeds under very mild reaction conditions, using an aryl α-diimine/Pd(II) catalyst and p-benzoquinone as oxidant, in the presence of a suitable alcohol. This process proved to be very efficient, selective and diastereospecific and various 2,3-disubstituted succinic esters have been obtained in high yields. In Chapter 3 the first bis-alkoxycarbonylation reaction of acrylic esters and acrylic amides, leading to the synthesis of 2-alkoxycarbonyl and 2-carbamoyl succinates respectively, is reported. Remarkably, the utilized aryl α-diimine/Pd(II) catalyst is able to promote the carbonylation of both the β- and the generally non-reactive α- positions of these alkenes. The proposed catalytic cycle is supported by DFT calculations. Section 2 is mainly focused on the Ni-catalyzed difunctionalization of unactivated alkenes tethered to unstabilized ketones. This reaction allows for a wide range of pharmaceutically useful cyclic architectures to be obtained. Chapter 4 consists of an introduction to the difunctionalization reactions of unactivated olefins. In particular, intramolecular reactions will be discussed in detail. In Chapter 5 the results obtained from the Ni-catalyzed difunctionalization of unactivated alkenes tethered to unstabilized ketones are reported. The reaction proceeds through the formation of a zinc-enolate compound, followed by a cyclization/cross-coupling reaction, which takes place in the presence of a phosphine/Ni(II) complex and an (hetero)aryl electrophile, leading to different cyclic and bicyilc architectures. In Chapter 6, preliminary results concerning the anionic cyclization of zinc enolates tethered to unactivated alkenes are presented.
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The thesis is divided into two main parts. In the first one organocatalysis is briefly introduced. Then, new enantiopure trityl pyrrolidines modified with an ionic tag are described. All the catalysts are tested in the benchmark Michael addition reaction to prove their activity and stereoselectivity. In the second part, photocatalysis is first introduced. Then, four different research projects are described. At first, the construction of a hybrid metal-organo-photoredox catalyst is described. The hybrid photocatalysts obtained were employed in the benchmark photoredox alkylation of aldehydes. Then, the use of visible light and a photocatalytic system for the cyclization of iodoaryl vinyl derivatives to tetrahydroquinoline structures is described. In addition, the reaction can also be performed using flow-chemistry. Finally, a mechanistic proposal based on some mechanistic studies is described. Third, a new photoredox catalyzed transformation for the synthesis of 2,3-dihydrofurans is reported. Depending on the involved starting materials, different pathways have arisen. A mechanistic proposal based on reported literatures and experimental data is described. At last, a new photoredox catalyzed transformation for the synthesis of 2-aminofurans is described. Electrophilic radical addition on allenamides and subsequential intramolecular cyclization are exploited. The reaction proceeds under very mild conditions and in 2-aminofurans are obtained in good to high yield. It represents one of the few applications of allenamides in photoredox catalysis. A mechanistic proposal is described. Finally, preliminary investigations on the applicability of the developed transformation under flow chemistry conditions.
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The topic of this thesis is the DFT computational study of the mechanisms for the synthesis of chiral 3,4,5-trisubstituted piperidines and 2,6-disubstituted morpholines. The goal of this synthesis is to use, the same substrate containing two electrophilic sites: an α,β-unsaturated ester and a ketone, which evolve according to the nucleophile used (cyanide, phenyl sulfide) through different addition and cyclization reactions. A quaternary ammonium salt is used as a catalyst for these reactions, which leads to a diastereoisomeric excess both for the reactions of morpholine and piperidine products. Studies in silico of the pathways of these reactions explain the chemoselection and diasteroselection deriving from the two nucleophiles used. In this case of piperidine products, it was also possible to validate the hypothesis of a concerted nucleophilic addition mechanism on the α,β-unsaturated site and cyclization due to an intramolecular Michael addition.