364 research outputs found

    Prolinamides as Asymmetric Organocatalysts

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    Producción CientíficaProlinamides are valuable organocatalysts for enantioselective transformations that occur by activation of the nucleophile by enamine formation. Different substituents can be appended on the nitrogen atom of the carboxamide, which allow for the modulation of the catalytic properties. In that way, the acidity, the hydrogen donor properties, the hydrophobicity, or the chiral environment can be modified, in a few steps, starting from easily available proline.Ministerio de Economía, Industria y Competitividad (CTQ2014-59870-P)Junta de Castilla y León (programa de apoyo a proyectos de investigación – Ref. VA064U13

    Concentração das firmas líderes de auditoria dentre as maiores empresas por setor : perspectiva do mercado nacional e medidas assertivas

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    Trabalho de Conclusão de Curso (graduação)—Universidade de Brasília, Faculdade de Economia, Administração, Contabilidade e Gestão de Políticas Públicas, Departamento de Ciências Contábeis e Atuariais, 2018.Tendo em vista o destaque dado à figura do auditor independente no desenvolvimento do mercado financeiro, no presente trabalho busca-se analisar o grau de concentração na prestação de serviço de auditoria para as maiores empresas do mercado em termos de receita líquida no período retroativo a 5 anos – 2013 a 2017. Coletados em sites institucionais ou junto ao órgão regulador, processam-se os dados referentes ao parecer de auditoria compilando-os em gráficos que transmitem a perspectiva percentual da participação das maiores firmas do ramo em diferentes seções. Enquadra-se como pesquisa descritiva tendo em vista que constata a característica de determinada população, nesse caso apresentando-se as maiores empresas por setor. Por etapa o trabalho estrutura-se da seguinte forma: introdução em que trata-se da contextualização do tema e objetivos traçados à pesquisa; metodologia aplicada; definição do grupo de amostragem considerado maiores empresas por setor, coleta eletrônica de pareceres, análise exploratória de dados com exposição em painel. Contemplamse quatro gráficos e três tabelas na pesquisa em que se evidencia a dominação do mercado pelas maiores firmas, alcançando 26 das 30 empresas em análise, tratando-se de momentos alternados no tempo expondo também ranking de maior carteira dentre as líderes do setor de auditoria independente. Na conclusão do trabalho referem-se aos dados expostos como perspectivas da consolidação no mercado nacional, evolução do cenário da concentração percebida e alternativas à concentração constatadas, mencionando ainda agenda positiva para os futuros trabalhos desenvolvidos a respeito do tema.In order to highlight the role of the independent auditor in the development of the financial market, the present work seeks to analyze the degree of concentration in the provision of audit service for the largest companies in the market in terms of net revenue in the retroactive period to 5 years - 2013 to 2017. Collected on institutional sites or with the regulatory body, the data related to the audit opinion are processed by compiling them in graphs that convey the percentage perspective of the participation of the largest firms in the different sections. It is described as a descriptive research, in view of the fact that the characteristic of a given population, in this case, presenting the largest companies by sector. By stage the work is structured in the following way: introduction in which it is the contextualization of the theme and objectives traced to the research; applied methodology; definition of the sampling group considered larger companies by sector, electronic collection of opinions, exploratory data analysis with panel exposure. There are four graphs and three tables in the survey, which show the domination of the market by the largest firms, reaching 26 of the 30 companies under analysis, with alternating moments in time, also exposing a ranking of the largest portfolio among the leaders of the sector independent audit. At the conclusion of the study, the data are presented as prospects for consolidation in the domestic market, evolution of the scenario of perceived concentration and alternatives to concentration found, also mentioning a positive agenda for future work on this subject

    Especificações técnicas para redes húmidas de combate a incêndios

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    Mestrado em Engenharia CivilO presente trabalho pretende enunciar propostas de melhoria das especificações técnicas para redes húmidas da atual legislação, na segurança contra incêndios em edifícios. Esta melhoria pretende levar ao aperfeiçoamento do funcionamento destas redes, redução do número de ocorrências, de vítimas de prejuízos materiais, patrimoniais e ambientais. A atual legislação prevê em muitas situações a obrigatoriedade da utilização de redes húmidas, no entanto esta encontra-se com insuficiência ou ausência de especificações técnicas sobre a conceção e o dimensionamento destes sistemas. São apresentadas as medidas e os meios de segurança aplicados atualmente, assim como a utilização das redes húmidas em edifícios de modo a entender melhor o funcionamento e a aplicabilidade destes sistemas. Com o objetivo de compreender outras normas, é feita uma análise comparativa com uma norma de referência internacional, a NFPA, (americana), e com a NTE (espanhola). Foram analisados diversos casos de estudo, com a finalidade de enunciar aspetos considerados positivos e menos corretos, apresentando propostas de melhoria e salientando especificações técnicas corretamente aplicadas. Através da análise comparativa das normas e dos casos de estudo, revela-se a importância de fazer uma atualização legislativa da segurança contra incêndios em edifícios, onde são apresentadas algumas sugestões.The present work intends to enunciate proposals for improvement of the technical specifications for wet risers of the current legislation, on fire safety in buildings. This work intends to improve functioning of these risers, reducing the number occurrences of environmental damage. The current law provides in many situations the mandatory use of wet risers, however has a lack of technical specifications on the design and dimensioning of these systems. Measures and safety means are presented, as well as the use of wet risers in buildings in order to better understand the operation and the applicability of these systems. In order to understand other standards, a comparative analysis regarding a standard of international reference, NFPA (American), and the NTE (Spanish) was carried out. Several case studies were analyzed, in order to enunciate positive aspects and less correct ones, with improvement proposals and highlighting correctly applied technical specifications. Through the comparative analysis of the standards and case studies, it reveals the importance of making a legislative update on fire safety in buildings is shown along with some suggestions

    The organocatalyzed domino Michael–aldol reaction revisited. Synthesis of enantioenriched 3-hydroxycyclohexanone derivatives by reaction of enals with α,α′-diaryl-substituted acetone

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    Producción CientíficaThe reaction of enals with α,α′-diaryl-substituted acetones (pKa > 18) catalyzed by (S)-1-(2-pyrrolidinylmethyl) pyrrolidine provides direct access to enantioenriched 2,5,6-trisubstituted-3-hydroxy cyclohexanones. The process constitutes a highly stereoselective organocatalytic tandem Michael-intramolecular aldol reaction. It has been demonstrated that the stereoselection is dependent on the reaction conditions because only syn diastereoisomers are able to cyclize, and that anti diastereoisomers participate in a retro-Michael process decreasing the enantioselection.Ministerio de Economía, Industria y Competitividad (CTQ 2011-28487)Junta de Castilla y León (programa de apoyo a proyectos de investigación – Ref. VA064U13)Universidad de Valladolid for a pre-doctoral fellowship

    One-pot Sequential Organocatalytic Michael-Tishchenko-Lactonization Reactions. Synthesis of Enantioenriched 4, 5, 6 -Trisubstituted - Lactones

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    Producción CientíficaEnantioenriched trisubstituted lactones were obtained in good yields and moderate to very good enantioselectivities in one-pot process, which implies a sequential organocatalyzed Michael addition of ketones to enals, followed by catalytic intramolecular diastereoselective Tishchenko reaction and lactonization. The final lactones were obtained as single diastereoisomers, demonstrating that the mixture of the anti and syn diastereomers epimerized to the syn hydroxy ester during the oxido-reduction step.Ministerio de Economía, Industria y Competitividad (CTQ 2011-28487)Junta de Castilla y León (programa de apoyo a proyectos de investigación – Ref. VA064U13)Universidad de Valladolid for a pre-doctoral fellowship

    Supported Bifunctional Chiral Thioureas as Catalysts in the Synthesis of 3‐Amino‐2‐Oxindoles through Enantioselective aza‐Friedel‐Crafts Reaction: Application in Continuous Flow Processes

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    Producción CientíficaSupported cinchone‐derived thioureas promote highly enantioselective aza‐Friedel‐Crafts reaction of different naphthols with a variety of N‐Boc ketimines derived from isatin. The catalysts are recoverable and reusable, and one of the supported catalysts has been used in a flow process allowing the synthesis of 3‐amino‐2‐oxindole derivatives in multigram scale with high yield and enantioselectivity.Junta de Castilla y León (programa de apoyo a proyectos de investigación - Ref. VA115P17)Junta de Castilla y León (programa de apoyo a proyectos de investigación - Ref. VA149G18

    Bifunctional thiourea-modified polymers of intrinsic microporosity for enantioselective α-amination of 3-aryl-2-oxindoles in batch and flow conditions

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    Producción CientíficaTwo novel polymers of intrinsic microporosity decorated with chiral thioureas have been used as recoverable organocatalysts in enantioselective α-amination of 3-aryl-substituted oxindoles, creating a quaternary stereocenter. Both catalysts were able to promote the reaction in excellent yields and good enantioselection. Catalyst II, with a pyridyl nucleus, was used in recycling experiments maintaining the activity without additional reactivation, and in flow processes allowing the synthesis of the amination product in multigram scale.Junta de Castilla y León (Projects FEDER VA115P17, and VA149G18
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