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.

Fighting the Strai(gh)tjacket: black women bonding in Loving Her and The Color Purple

O objetivo deste trabalho é analisar como as relações lésbicas são retratadas nas obras Loving Her e The Color Purple. Ao analisar as relações entre homens/mulheres e mulheres/mulheres, este estudo também revê e critica o golpe triplo sofrido por lésbicas negras, por serem, ao mesmo tempo, mulheres, afro-americanas e homossexuais. Utilizando fatos históricos para situar as obras em um contexto social, além da teoria do lesbian continuum afim de atestar a riqueza e diversidade do laço afetivo entre mulheres, este trabalho vem por desmistificar as noções simplistas em relação à literatura lésbica Afro-Americana, afugentando a sombra que pairava sobre o tabu e elevando a mulher negra, lésbica ou não, a seu lugar de direito na sociedade

The interaction of color and luminance in stereoscopic vision

Experiments are described using the random dot stereo patterns devised by Julesz, but substituting various colors and luminances for the usual black and white random squares. The ability to perceive the patterns in depth depends on a luminance difference between the colors used. If two colors are the same luminance, then depth is not perceived although each of the individual squares which make up the patterns is easily seen due to the color difference. This is true for any combination of different colors. If different colors are used for corresponding random squares between the left and right eye patterns, stereopsis is possible for all combinations of binocular rivalry in color, provided the luminance difference is large enough. Rivalry in luminance always precludes stereopsis, regardless of the colors involved.

Multicolor luminescence in oxygen-deficient Tb3+;doped calcium aluminogermanate glasses

In this paper, we report on the multicolor luminescence in oxygen-deficient Tb3+-doped calcium aluminogermanate glasses. A simple method was proposed to control oxygen-deficient defects in glasses by adding metal Al instead of the corresponding oxide (Al2O3), resulting in efficient blue and red emissions from Tb3+-undoped glasses with 300 and 380 nm excitation wavelengths, respectively. Moreover, in Tb3+-doped oxygen-deficient glasses, bright three-color (sky-blue, green or yellow, and red) luminescence was observed with 300, 380, and 395 nm excitation wavelengths, respectively. These glasses are useful for the fabrication of white light-emitting diode (LED) lighting.

The labour market in the Basque Country: University Employment Centers

This project is a study of the Labour Market in the Basque Country. First of all, we have analysed the position of the Basque Country in the European Union employment situation by gender and age. Secondly, we have studied the educational level of the Basque Country from the European Union perspective. Thirdly, we have showed the importance of labour orientation in educational level, especially in higher education. Finally, the design of new employment policies to promote the creation of jobs and stability of the labour market depends on: new industries and university employment policies.

Design and fabrication of color filters for projection display system

Color filters are key components in an optical engine projection display system. In this paper, a new admittance-matching method for designing and fabricating the high performance filters is described, in which the optimized layers are limited to the interfaces between the stack (each combination of quarter-wave-optical-thickness film layers is called a stack) and stack, or between stack and substrate, or between stack and incident medium. This method works well in designing filters containing multiple stacks such as UV-IR cut and broadband filters. The tolerance and angle sensitivity for the designed film stacks are analyzed. The thermal stability of the sample color filters was measured. A good result in optical performance and thermal stability was obtained through the new design approach. (c) 2006 Society of Photo-Optical Instrumentation Engineers.

Design and fabrication of color filters for projection display system

Color filters are key components in an optical engine projection display system. In this paper, a new admittance-matching method for designing and fabricating the high performance filters is described, in which the optimized layers are limited to the interfaces between the stack (each combination of quarter-wave-optical-thickness film layers is called a stack) and stack, or between stack and substrate, or between stack and incident medium. This method works well in designing filters containing multiple stacks such as UV-IR cut and broadband filters. The tolerance and angle sensitivity for the designed film stacks are analyzed. The thermal stability of the sample color filters was measured. A good result in optical performance and thermal stability was obtained through the new design approach. (c) 2006 Society of Photo-Optical Instrumentation Engineers.