Strategies for the Stereoselective Synthesis of Carbon Quaternary Centers via Transition Metal-Catalyzed Alkylation of Enolate Compounds

Notwithstanding advances in modern chemical methods, the selective installation of sterically encumbered carbon stereocenters, in particular all-carbon quaternary centers, remains an unsolved problem in organic chemistry. The prevalence of all-carbon quaternary centers in biologically active natural products and pharmaceutical compounds provides a strong impetus to address current limitations in the state of the art of their generation. This thesis presents four related projects, all of which share in the goal of constructing highly-congested carbon centers in a stereoselective manner, and in the use of transition-metal catalyzed alkylation as a means to address that goal.

The first research described is an extension of allylic alkylation methodology previously developed in the Stoltz group to small, strained rings. This research constitutes the first transition metal-catalyzed enantioselective α-alkylation of cyclobutanones. Under Pd-catalysis, this chemistry affords all–carbon α-quaternary cyclobutanones in good to excellent yields and enantioselectivities.

Next is described our development of a (trimethylsilyl)ethyl β-ketoester class of enolate precursors, and their application in palladium–catalyzed asymmetric allylic alkylation to yield a variety of α-quaternary ketones and lactams. Independent coupling partner synthesis engenders enhanced allyl substrate scope relative to allyl β-ketoester substrates; highly functionalized α-quaternary ketones generated by the union of our fluoride-triggered β-ketoesters and sensitive allylic alkylation coupling partners serve to demonstrate the utility of this method for complex fragment coupling.

Lastly, our development of an Ir-catalyzed asymmetric allylic alkylation of cyclic β-ketoesters to afford highly congested, vicinal stereocenters comprised of tertiary and all-carbon quaternary centers with outstanding regio-, diastereo-, and enantiocontrol is detailed. Implementation of a subsequent Pd-catalyzed alkylation affords dialkylated products with pinpoint stereochemical control of both chiral centers. The chemistry is then extended to include acyclic β-ketoesters and similar levels of selective and functional group tolerance are observed. Critical to the successful development of this method was the employment of iridium catalysis in concert with N-aryl-phosphoramidite ligands.

Distribution of Oreochromis niloticus (L.) in the Ugandan waters of Lake Victoria

The Lake Victoria fish fauna was dominated by cichlids before the establishment of the exotic species Oreochromis niloticus (L.) and Latus niloticus (L.). With the alterations in the ecology of Lake Victoria, changes may be expected to occur in the population dynamics of the fish species. In two zones of Lake Victoria, the size structure, distribution and abundance, condition factors, length-weight relationship and sex ratios of O. niloticus were determined. Larger fish were found in zone II than in zone III, where very few larger fish were recorded. More O. niloticus were caught in zone III, especially in Itome Bay, than in zone II but catch by weight was greater in zone II. More males than females were encountered in both zones. Oreochromis niloticus had similar condition factors in both zones.

Anomalous electric dipole internal conversion

Electric dipole internal conversion has been experimentally studied for several nuclei in the rare earth region. Anomalies in the conversion process have been interpreted in terms of nuclear structure effects. It was found that all the experimental results could be interpreted in terms of the j ∙ r type of penetration matrix element; the j ∙ ∇ type of penetration matrix element was not important. The ratio λ of the El j ∙ r penetration matrix element to the El gamma-ray matrix element was determined from the experiments to be:

Lu¹⁷⁵,396 keV, λ = - 1000 ± 100;

282 keV, λ = 500 ± 100;

144 keV, λ = 500 ± 250;

Hf¹⁷⁷, 321 keV λ = - 1400 ± 200;

208 keV λ = - 90 ± 40;

72 keV |λ| ≤ 650;

Gd¹⁵⁵, 86 keV λ = - 150 ± 100;

Tm¹⁶⁹, 63 keV λ = - 100 ± 100;

W¹⁸², 152 keV, λ = - 160 ±80;

67 keV, λ = - 100 ± 100.

Predictions for λ are made using the unified nuclear model.

Isotope shift studies in the rare earths and lead

Isotope shifts of K_α1 x-ray transitions were measured for the Neodymium isotopes Nd 142, 143, 144, 145, 146, 148 and 150, the Samarium isotopes Sm 147, 148, 149, 150, 152 and 154, the Gadolinium isotopes Gd 154, 155, 156, 157, 158 and 160, the Dysprosium isotopes Dy 162 and 164, the Erbium isotopes Er 166, 168 and 170, the Hafnium isotopes Hf 178 and 180 and the Lead isotopes Pb 204, 206, 207 and 208. A curved crystal Cauchois spectrometer was used. The analysis of the measurement furnished the variation of the mean square charge radius of the nucleus, δ˂r²˃, for 23 isotope pairs. The experimental results were compared with theoretical values from nuclear models. Combining the x-ray shifts and the optical shifts in Nd and Sm yielded the optical mass shifts. An anomaly was observed in the odd-even shifts when the optical and the x-ray shifts were plotted against each other.

Molecular ecology of european mustelids: Unraveling evolutionary and ecological patterns in Martes and Lutra genera

208 p.

O Trabalho na produção intelectual em Saúde Coletiva: uma análise da experiência brasileira de 1990 a 2008

A presente dissertação focaliza a produção intelectual no tema do trabalho, realizada sob a forma de dissertações de mestrado e teses de dutorado defendidas entre 1990 e 2008. Na pesquisa, deu-se prioridade à produção em Saúde Coletiva, sendo investigados 25 centros de pesquisa filiados à ABRASCO (Associação Brasileira de Saúde Coletiva). Foi possível identificar, entre 1990 e 2008, um total de 564 produções acadêmicas distribuídas entre dissertações de mestrado e teses de doutorado. Desta produção, 75% são dissertações e 25%, teses. A produção total apresentou-se concentrada nos Estados de São Paulo (221 publicações) e Rio de Janeiro (208 publicações), compondo juntos 76% de toda a produção no país. As cinco universidades que mais se destacam na produção da área são: FIOCRUZ (Fundação Oswaldo Cruz), com 26,06% da produção nacional; USP (Universidade de São Paulo), com 18,79%; UNICAMP (Universidade de Campinas), com 14,54%; UFBA (Universidade Federal da Bahia), com 7,98% e UERJ (Universidade do Estado do Rio de Janeiro), com 6,56%. Além da produção espacial, as dissertações e teses foram classificadas por áreas temáticas, sendo classificadas em 13 descritores. Os resultados revelam uma concentração nas áreas de saúde do trabalhador, higiene e segurança no trabalho e recursos humanos. Temas referentes a trabalho e desenvolvimento tecnológico; emprego e renda; mudanças nas relações de trabalho; qualidade de vida e trabalho, gênero e saúde foram identificados como os de mais baixa densidade. Esses segmentos constituem lacunas a serem superadas por centros não-hegemônicos. Uma sugestão é a consolidação de linhas de pesquisa, por meio de alianças institucionais em torno de temas com baixa produção. As instituições com índices menores de publicação podem concentrar seus esforços em uma expansão da produção no tema do trabalho, garantindo um crescimento e a desconcentração da produção intelectual do Brasil.

Dorsch-Selektionsexperimente mit Grundschleppnetzen in der Ostsee

Teilergebnisse der 162. Reise des FFS "Anton Dohrn"

双频激光干涉仪的最大可测量速度研究

现代制造业对双频激光干涉仪的最大可测量速度提出了越来越高的要求。最大可测量速度是双频激光干涉仪的一项重要指标，它主要受双频激光光源所输出的频差、干涉仪的光学结构以及电子带宽等因素的限制。本文从理论和实验两方面对干涉仪的最大可测量速度进行了研究，搭建了基于自由落体运动的实验装置。实验结果表明，实际最大可测量速度略低于其理论值。另外，文中还分析了上述三种因素对最大可测量速度的影响。实验装置和结果可供工业应用提供参考。

Exploring new labelling strategies for boronated compounds: towards fast development and efficient assessment of BNCT drug candidates

208 p.