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.

Morphological variation with interspecific implications in a population of Sigara dorsalis (Leach) (Hemiptera Heteroptera: Corixidae), and a request for British specimens

Sigara dorsalis belongs to a very closely related group of six species forming the sub-genus Sigara sensu strictu. Each of the six species has a distinct allopatric geographical distribution in Europe. Studies were started on a series of populations in the north west Midlands of England. All the populations examined, except one, contained only males with the typical diagnostic features of S. dorsalis, albeit with considerable variation. One pond near Congleton, Cheshire situated in a permanent-ley pasture and apparently free from pollution contained typical S. dorsalis males but, in addition, many atypical individuals. From one sample of forty-six males, all possessed left parameres with the slight point on the dorsal surface characteristic of S. dorsalis. However, almost half possessed additional morphological features intermediate between S. dorsalis and S. striata.

The identification of British adult specimens of Sigara lateralis (Leach), Sigara concinna (Fieber), Callicorixa praeusta (Fieber) and Callicorixa wollastoni (Douglas & Scott) (Hemiptera Heteroptera: Corixidae)

The aim of this communication is to briefly review nomenclature in the genus Callicorixa, describe the variation in the dark markings on the posterior legs of all four species, describe alternative diagnostic features, and provide a key to identification based on these alternative features. Attention is also drawn to a small error in FBA Scientific Publication 50 (Adults of the British aquatic Hemiptera Heteroptera: a key with ecological notes).

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

Breeding populations of seabirds in California, 1989-1991. Volume I - population estimates

In 1989-1991, the U.S. Fish and Wildlife Service surveyed breeding populations of seabirds on the entire California coast. This study was sponsored by the Minerals Management Service in relation to outer continental shelf oil and gas leasing. At 483 nesting sites (excluding terns and skimmers in southern California), we estimated 643,307 breeding birds of 21 seabird species including: 410 Fork-tailed Storm-petrel (Oceanodroma furcata); 12,551 Leach's Storm-petrel (O. leucorhoa); 7,209 Ashy Storm-petrel (O. homochroa); 274 Black Storm-petrel (O. melania); 11,916 Brown Pelican (Pelecanus occidentalis); 10,037 Double-crested Cormorant (Phalacrocorax auritus); 83,394 Brandt's Cormorant (P. penicillatus); 14,345 Pelagic Cormorant (P. pelagicus); 888 Black Oystercatcher (Haemotopus bachmani); 4,764 California Gull (Larus californicus); 61,760 Western Gull (L. occidentalis); 2,838 Caspian Tern (Sterna caspia) (excluding southern California); 3,550 Forster's Tern (S. forsteri) (excluding southern California); 272 Least Tern (S. albifrons) (excluding southern California); 351,336 Common Murre (Uria aalge); 15,470 Pigeon Guillemot (Cepphus columba); 1,821 Marbled Murrelet (Brachyramphus marmoratus); 1,760 Xantus' Murrelet (Endomychura hypoleuca); 56,562 Cassin's Auklet (Ptychoramphus aleuticus); 1,769 Rhinoceros Auklet (Cerorhinca monocerata); and 276 Tufted Puffin (Fratercula cirrhata). The inland, historical or hybrid breeding status of American White Pelican (P. erythrorynchus), American Oystercatcher (H. palliatus), Heermann's Gull (L. heermanni), Ring-billed Gull (L. delawarensis), Glaucous-winged Gull (L. glaucescens) and Black Tern (Chlidonias niger) are discussed. Estimates for Gull-billed Tern (S. nilotica), Royal Tern (S. maxima), Elegant Tern (S. elegans) and Black Skimmer (Rhynchops niger) will be included in the final draft of this report. Overall numbers were slightly lower than reported in 1975-1980 surveys (summarized in Sowls et al. 1980. Catalog of California seabird colonies. U.S. Dept. Int., Fish Wildl. Serv., Biol. Serv. Prog., FWS/OBS 37/80). Recent declines were found or suspected for Fork-tailed Storm-petrel, Leach's Storm-petrel, White Pelican, Black Tern, Caspian Tern, Least Tern, Common Murre and Marbled Murrelet. Recent increases were found or suspected for Brown Pelican, Double-crested cormorant, California Gull, Western Gull, Forster's Tern and Rhinoceros Auklet. Similar numbers were found for other species or trends could not be determined without additional surveys, studies and/or more in-depth comparisons with previous surveys. The status of terns and skimmers in southern California has not yet been finalized.

Nuclear transfer in leach (Paramisgurnus dabryanus Sauvage) by cell-to-cell electrofusion

To study nuclear transfer in the leach (Paramisgurnus dabryanus Sauvage), blastula and gastrula cells were fused with UV-inactivated oocytes by cell-to-cell electrofusion. To facilitate nuclear transfer, blastula and gastrula cells were cultured or incubated at 4 degreesC in different solutions. TC-199 medium supplemented with 20% calf serum was the best culture solution, and effectively retained the totipotence of blastula or gastrula cells for up to 10 days, It was found that gastrula cells incubated at 4 degreesC had the same totipotence as blastula cells, The optimal UV dosage for inactivation of the oocyte chromatin was 180-240 mJ cm(-2). Electrofusion was carried out in a cone-shaped fusion chamber, which permitted the recipient oocyte and the donor blastula cell to contact one another. The electrofusion procedure resulted in a 10% success rate of normal-appearing fish. Genetic analysis indicated that the nuclear material originated from the donor cell (blastomere) and the oocyte pronucleus did not take part in development.

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...

Competitiveness in a globalised world: Michael Porter on the microeconomic foundations of the competitiveness of nations, regions, and firms.

In this paper, we provide the text of an interview with Professor Michael Porter discussing his research and ideas relating to the microeconomic foundations of global competitiveness. The discussion provides a microeconomic perspective on some of the key issues relating to recent research on competitiveness, productivity, clusters, US economic leadership, economic growth and development.