Synthetic scope and DFT analysis of the chiral binap-gold(I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes

he 1,3-dipolar cycloaddition between glycine-derived azlactones with maleimides is efficiently catalyzed by the dimeric chiral complex [(S-a)-Binap.AuTFA](2). The alanine-derived oxazolone only reacts with tert-butyl acrylate giving anomalous regiochemistry, which is explained and supported by Natural Resonance Theory and Nucleus Independent Chemical Shifts calculations. The origin of the high enantiodiscrimination observed with maleimides and tert-butyl acrylate is analyzed using DFT computed at M06/Lanl2dz//ONIOM(b3lyp/Lanl2dz:UFF) level. Several applications of these cycloadducts in the synthesis of new proline derivatives with a 2,5-trans-arrangement and in the preparation of complex fused polycyclic molecules are described.

Chiral gold(I) vs chiral silver complexes as catalysts for the enantioselective synthesis of the second generation GSK-hepatitis C virus inhibitor

The synthesis of a GSK 2(nd) generation inhibitor of the hepatitis C virus, by enantioselective 1,3-dipolar cycloaddition between a leucine derived iminoester and tert-butyl acrylate, was studied. The comparison between silver(I) and gold(I) catalysts in this reaction was established by working with chiral phosphoramidites or with chiral BINAP. The best reaction conditions were used for the total synthesis of the hepatitis C virus inhibitor by a four step procedure affording this product in 99% ee and in 63% overall yield. The origin of the enantioselectivity of the chiral gold(I) catalyst was justified according to DFT calculations, the stabilizing coulombic interaction between the nitrogen atom of the thiazole moiety and one of the gold atoms being crucial.

Funtzio sintaktikoen gold estandarra eskuz etiketatzeko gidalerroak

[EN]In this report we present the tags we use when annotating the gold standard of syntactic functions and the decisions taken during its annotation. The gold standard is a necessary resource to evaluate the rulebased surface syntactic parser (the one based on the Constraint Grammar formalism), and, moreover, it can be useful to develop and evaluate statistical parsers. The tags we are presenting here follow the Constraint Grammar (CG) formalism (Karlsson et al., 1995). In fact, last experiments show that good results have been obtained when parsing with CG (Karlsson et al., 1995; Samuelsson and Voutilainen,1997; Tapanainen and Järvinen, 1997; Bick, 2000).

Financial Futures Markets and Their Impact on the Real Economy in Middle and Low Income Countries

This project analyses the influence of the futures market on middle and low income countries. In it, I attempt to show that investments made by large investment funds in this market, as well as by certain pension plans, bring major consequences whose effects are more evident in less developed countries. The cornerstones of the work are as follows; to attempt to see the existing relationship between the commodity futures market and its underlying assets; analysing products such as wheat, rice and corn in-depth, because these are the most basic foodstuffs at a global level; to determine how an increase in trading in these markets can affect the lives of people in the poorest countries; to analyse investor concern regarding the consequences that their investments may have. Throughout the project we will see how large speculators use production forecasting models to determine the shortage of a commodity in order to take a position in the futures market to profit from it. In addition we will see how an increase in trading in this market causes an increase in the price of the underlying asset in the spot market. As for investor concern, I can say it is negligible, but the idea of running pension plans or investment funds that follow some social criteria has been welcomed by those interviewed, which makes me think that different legislation is possible. This legislation will only come into existence if it is demanded by the people. A fact that now becomes complicated because without a minimum financial basis, they cannot even know how the large investment funds trade with hunger in the world. The day when most people understand how large speculators profit from famine will be the day to put pressure on governments to begin to put limits on speculation. This makes financial awareness necessary in order to achieve a curb in excessive speculation.

Giant diamagnetism of gold nanorods

The presence of giant diamagnetism in Au nanorods, NRs, is shown to be a possible consequence of field induced currents in the surface electrons. The distance, Delta , between quantum surface energy levels has been calculated as a function of the NRs radius. Note that those electrons occupying states for which Delta > k(B)T are steadily orbiting with constant orbital moment. The diamagnetic response induced when a field is turned on remains constant during the time the field is acting. As the NRs radius increases, Delta decreases and accordingly the electron fraction available to generate constant currents decreases, consequently the surface diamagnetic susceptibility decreases towards its bulk value. The surface electronic motion induced by the axial applied field on electrons confined into a cylindrical surface accounts with extremely good quantitative agreement for the giant diamagnetism recently measured and reported.

Gold Standard and Reforms of The International Monetary System

This academic work is based on the study of the gold standard, its evolution over the years, their periods of boom and crisis. We will also discuss the arguments that some economists back the return to this monetary system.