Activación de aldehídos a,b-insaturados mediante aminocatálisis en procesos enantioselectivos. Cicloadiciones (3+2) y reacciones en cascada Michael/Henry

During the research that it is summarized in the present memory, the activation of enals via iminium ion catalysis in different transformations has been studied. Firstly, a 1,3-dipolar cycloaddition between stable azomethine ylides and a,b-unsaturated aldehydes catalyzed by a chiral imidazolidinone derivative has been optimized. Employing this methodology we have synthesized a large range of densely substituted pyrroloisoquinolines and pyrrolophthalazines with good yields and high values of diastereo- and enantioselectivity. Moreover, a mechanistic study has been carried out based on DFT calculations and experimental data which have allowed us to propose that the (3+2) cycloaddition reaction follows a sequential Michael addition/Mannich cyclization pathway. The formation of the iminium ion as a result of the condensation between the a,b-unsaturated aldehyde and the catalyst plays an essential role, regarding both reactivity and stereoselectivity. On the other hand we have developed a methodology to carry out a cascade Michael/Henry reaction followed by a sequential dehydration. Starting from simple substrates (2-nitromethylacrilates and a,b-unsaturated aldehydes) and employing a prolinol-derivative catalyst a series of quiral nitrocyclohexadienes have been synthesized.

Relatorio e synopse dos trabalhos da Camara dos Srs. Deputados : na sessão do anno de 1886 : contendo andamento de todos os projetos e pareceres, discussão especificada do orçamento e prorogativa, differentes documentos, quadros estatisticos e outros esclarecimentos : organizados na Secretaria da mesma Camara

Sinopse dos trabalhos da Câmara dos Deputados, em 1887.

Chapingo: Capela

Essa dissertação é uma proposta de releitura do conjunto de murais no interior da Capela de Chapingo, México. Tal releitura de crítica artística relaciona-se à apropriação de uma metodologia derivada da própria noção de capela, metodologia essa que compactua com o ambiente artístico em questão e com a fenomenologia do contemplador desse conjunto. O objetivo dessa proposta é apresentar as nuances envolvidas no conceito-chave, por parte da historiografia artístico-religiosa, de suporte-capela, isto é, a capela não apenas como ambiente religioso, mas como ocasião artística

Holding mirrors up to Hamlet: what Franco Zeffirellis and Michael Almereydas filmic adaptations of the play tell us about it

Hamlet (1601), de William Shakespeare, é, desde o Fólio de 1623, circundada por um enorme e variado volume de leituras, que abrangem desde textos críticos e teóricos até as mais diversas adaptações teatrais e cinematográficas. Desde o final do século 19, o cinema vem adaptando peças de Shakespeare, fornecendo novos pontos de vista e sugestões para a encenação dessa obra ao levá-la inúmeras vezes para as telas. Dentre uma longa lista de adaptações fílmicas de Hamlet, o Hamlet mainstream de Franco Zeffirelli (1990) e o Hamlet 2000 (2000), filme independente de Michael Almereyda, compõem o corpus eleito para análise nesta dissertação. Dialogando com noções de críticos e teóricos que desenvolveram estudos sobre o conceito de adaptação, tais como André Bazin, Robert Stam e Linda Hutcheon, sugiro uma desierarquização entre a peça shakespeariana e os filmes logo, entre literatura/teatro e cinema. O objetivo final deste trabalho encontra-se na proposta de uma reflexão sobre esses filmes enquanto potenciais materiais críticos elucidativos para o estudo da peça, úteis na discussão de alguns de seus mais importantes temas e/ou questões

A study on length-weight relationship, food and feeding habits of Indian scad, Decapterus russelli (Ruppel, 1830) along the northwest coast of India

Length and weight relationship of Decapterus russelli (Ruppell, 1830) is worked out to be W = 0.00312 L³ which indicates the isometric growth of the fish. Study on food and feeding habits revealed that the species is carnivorous, pelagic, feeding primarily on small crustaceans and small fish species, viz. Acetes indicus, ostracods, Apogon sp., Leiognathus sp., sciaenids, Netnipterus japonicas, Myctophid sp., Trichiurus sp., Therapon sp., D.russelli and occasionally on prawns. It is a selective feeder on Aeetes indicus.

Some aspects of the biology of Johnieops sina (Cuvier, 1830) from Mumbai waters

Investigations on food and feeding of Johnieops sina indicated that it feeds mainly on penaeid prawns, Acetes spp. and fishes. Penaeid prawns were found to be its preferred food item. The spawning activity was observed throughout the year with two peaks in February and August, supported by prominent peaks of gonadosomatic index in the same months. The minimum size at first maturity for females was 153 mm. The absolute fecundity ranged from 28,495 to 135,346 eggs for the ovaries weighing 1.30 to 9.49 g.

Efficient synthesis of α-alkylidene-β-lactams via NaOH-promoted intramolecular aza-Michael addition of α-carbamoyl ketene-S,S-acetals in aqueous media

A facile and efficient synthesis of substituted alpha-alkylidene-beta-lactams have been developed via a NaOH-promoted intramolecular aza-Michael addition of alpha-carbamoyl, alpha-(1-chlorovinyl) ketene-S,S-acetals and subsequent nucleophilic vinylic substitution (SNV) reaction in alcoholic aqueous media. (C) 2008 Elsevier Ltd. All rights reserved.

Highly efficient and recoverable dendritic organocatalyst from click chemistry for the asymmetric michael addition of ketones to nitroolefins without the use of organic solvent

A series Of pyrrolidine-triazole based dendritic catalysts have been synthesized and applied directly in the asymmetric Michael addition of ketones to nitroolefins without the use of an organic solvent. Good yields (up to 99%), and high diastereoselectivities (up to syn/anti = 45:1) and enantioselectivities (up to 95% ee) have been obtained. Furthermore. the third generation catalyst can be reused at least five times without significant loss of catalytic activity. (C) 2008 Elsevier Ltd. All rights reserved.

Asymmetric Michael addition of aldehydes to nitroolefins catalyzed by L-prolinamide derivatives using phenols as co-catalysts

The asymmetric Michael addition of aldehydes to nitroolefins was investigated using L-prolinamide derivatives of 2-(2'-piperidinyl)pyridine as catalyst and a variety of phenols as co-catalyst. Extensive screening toward the effect of prolinamides, phenols, and solvents on this transformation revealed that a combination of (S)-2-(2'-piperidinyl)pyridine-derived trans-4-hydroxy-L-prolinamide 2c, (S)-1,1'-bi-2-naphthol, and dichloromethane was a promising system. This system was shown to be amenable to a rich variety of aldehydes and nitroolefins and afforded the nitroaldehyde products with excellent yield, enantiomeric excess (up to 99%) and diastereoselectivity ratio (up to 99/1), even in the case of 1 mol % catalyst loading and 1.5 equiv of aldehydes.

Facile synthesis and characterization of hyperbranched poly(ether amide)s generated from Michael addition polymerization of in situ created AB(2) monomers

A new straightforward strategy for synthesis of novel hyperbranched poly (ether amide)s from readily available monomers has been developed. By optimizing the reaction conditions, the AB(2)-type monomers were formed dominantly during the initial reaction stage. Without any purification, the AB(2) intermediate was subjected to further polymerization in the presence (or absence) of an initiator, to prepare the hyperbranched polymer-bearing multihydroxyl end-groups. The influence of monomer, initiator, and solvent on polymerization and the molecular weight (MW) of the resultant polymers was studied thoroughly. The MALDI-TOF MS of the polymers indicated that the polymerization proceeded in the proposed way. Analyses of H-1 NMR and C-13 NMR spectra revealed the branched structures of the polymers obtained. These polymers exhibit high-moderate MWs and broad MW distributions determined by gel permeation chromatography (GPC) in combination with triple detectors, including refractive index, light scattering, and viscosity detectors. In addition, the examination of the solution behavior of these polymers showed that the values of intrinsic viscosity [eta] and the Mark-Houwink exponent a were remarkably lower compared with their linear analogs, because of their branched nature.

Thia-michael addition reactions in water using 3-[Bis(alkylthio) methylene]pentane-2,4-diones as odorless and efficient thiol equivalents

3-[Bis(ethylthio)methylene]pentane-2,4-dione (1a) and 3-[bis(benzylthio)methylene]pentane-2,4-dione (1b) have been investigated as non-thiolic and odorless thiol equivalents in thia-Michael addition reactions. In the presence of aqueous p-dodecyl benzenesulfonic acid (DBSA), compound (1) was cleaved and the generated thiols underwent facile conjugate addition to alpha,beta-unsaturated ketones 2 in-situ, affording the corresponding beta-keto sulfides (3) in good yields.

含分子内氢键的苯硫酚在水相中的Michael加成反应

苯硫酚的巯基是一个较强的亲核基团 [1] ,对 α,β-不饱和双键的 Michael加成反应已有报道 [2～ 4 ] .但是当巯基的邻位存在与其形成氢键的基团时 ,如果按文献条件进行反应 ,或者反应无法进行 [5,6 ] ,或者要使用反应条件苛刻的丁基锂 [6 ] ,或者使用吡啶等毒性较大的反应溶剂 [2～ 9] ,而且产率较低 .本文选择了饱和碳酸氢钠水溶液 /n-四丁基硫酸氢铵的反应条件 ,探讨了该类化合物在此条件下的 Michael加成反应 .以 3个含分子内氢键的苯硫酚 (邻羟基苯硫酚、邻氨基苯硫酚和邻羧基苯硫酚 )为起始物 ,对丙烯酸乙酯和丙烯腈进行了 Michael加成反应 .本方法的特点在于不使用特殊的有机溶剂 ,反应在水相[10～ 12 ] 中进行 ;反应速度快 ,收率高 ,无巯基偶联 [13] 副产物生成 .反应式如 Scheme1所示 .RSH1 a— 1 c+ OONa HCO3,H2 On-Bu4 N HSO4RSOO2 a— 2 cRSH1 a— 1 c+ NC Na HCO3,H2 On-Bu4 N HSO4RSCN3 a— 3 ca. R =OH;b. R =N H2 ;c. R...

Ocorrência de Aleurothrixus aepim (Goeldi, 1886) (Hemiptera: Aleyrodidae) em Cruz das Almas, BA.

As moscas-brancas são pragas tanto de plantas ornamentais como de cultivos, sendo encontradas em quase todas as regiões onde se cultiva a mandioca. Nessa cultura, já foram identificadas as espécies Aleurotrachelus socialis, Aleurodicus dispersus, Aleurothrixus aepim, Aleuronudus sp., Bemisia tabaci, B. tuberculata, B. afer, Paraleyrodes sp., Trialeurodes abutilonea, T. variabilis e Tetraleurodes sp. Esses pequenos insetos são facilmente reconhecíveis, visto que em geral as populações dos adultos podem ser detectadas sacudindo os brotos das plantas para fazê-los voar, enquanto a fase jovem pode ser encontrada na face inferior das folhas basais e medianas.