Rearrangement of 3-Acyl Derivatives of L-Ascorbic Acid

Abstract

Evidence of rearrangement of 3-acyl derivatives of ascorbic acid to 2-acyl derivatives has been found for carbon and phosphorus acyl groups. The observations are consistent with intramolecular rearrangement through a cyclic intermediate in which the acyl group is bonded to both the 2- and 3-oxygen atoms of ascorbic acid. A rate of rearrangement has been measured for the 3-diphenylphosphinate ester. Calculated results indicate an increase in negative atomic charge at O-2 in the 3-acyl esters but a decrease in the charge of O-3 in the 2-acyl esters.     

Hiv-1 Specific Reverse Transcriptase Inhibitors: why are Tsao-Nucleosides so Unique?

1. INTRODUCTION

AIDS will still be one of the most important challenges for the Scientific Community in the approaching new century. Since the identification, in 1983-84,^1,2 of human immunodeficiency virus (HIV) as the etiological agent of AIDS, significant progress has been made in the treatment of HIV-infected patients. This has been in part due to the discovery and clinical use of an increasing number of anti-HIV drugs. However, while highly active antiretroviral therapy (HAART)³ approaches have reduced the morbidity and mortality, the intertwined problems of drug induced viral resistance, poor compliance with complex regimens and therapy failure continue. Therefore, there remains a pressing need for the development of new antiviral agents that can be used not only as first line therapeutic candidates, but also in the antiretroviral-experienced patient population.     

Multivariate optimization of the Kharasch–Sosnovsky allylic oxidation of olefins

The multivariate optimization method known as simplex is applied to the Kharasch–Sosnovsky allylic oxidation of double bonds. By applying this method, the amounts of three variables (copper source, oxidant, and additive) are optimized at the same time. Under the conditions thus obtained the reaction takes place in a considerable shorter time, being the alkene the limiting reagent. These conditions are applied to some monoterpenes and sesquiterpenes leading regioselectively to the corresponding benzoate esters, opening a route to the employment of this reaction in the synthesis of more complex molecules.     

Directed ortho-lithiation of unprotected diphenylphosphinic acids

Directed ortho lithiation of diphenylphosphinic acid and subsequent electrophilic trapping provides mono ortho-functionalized derivatives including enantiopure γ-aminophosphinic acids in moderate yields. Copper catalyzed coupling of the ortho anion leads to biphenyl-2,2′-diylbis(phenylphosphinic acid), a phosphorus analogue of biphenyl-2,2′-dicarboxylic acid. Preliminary studies of the metal-binding abilities of this O,O-chelating ligand towards a series of metal cations are included.     

Calculation of the HOMA model parameters for the carbon–boron bond

An extension of the harmonic oscillator model of aromaticity (HOMA) model to systems with carbon–boron bonds is presented. Model parameters were estimated using experimental and theoretical bond lengths. It is shown that both approaches produce very similar HOMA models. In the second part of the article, the aromaticity levels of several model compounds containing carbon–boron bonds are calculated using the previously obtained parameters. The results of these calculations are compared with those provided by other aromaticity indices. The aromaticity of boron-containing compounds is also compared with the aromaticity of analogous compounds containing carbon and nitrogen.     

Density Functional Theory Study of Hypoxanthine Tautomerism in Both the Isolated State and a Modeled-Ideal Aqueous Solution at Several Heterocyclic Protonation Levels

In order to advance the knowledge of prototropic tautomerism from the physicochemical point of view, the purine derivative hypoxanthine has been selected and studied. The overall purpose has been to explore thermodynamic aspects of the heterocycle tautomerism under the influence of both its protonation level and the surrounding dielectric constant. A Density Functional Theory study (at the B3LYP/6-31++G** level) was performed, in which the energetic and thermodynamic stabilities, the electric dipole moment values, the tautomeric equilibrium constants and the tautomeric populations were obtained for several hypoxanthine tautomers under systematically modified heterocyclic protonation levels, considering both isolated and ideal aqueous solution states. Among the interesting results obtained are changes in the tautomeric populations for several heterocyclic protonation states and with the increase of the dielectric constant. Several of the predictions made for an aqueous solution show good agreement with recently reported experimental conclusions. Also, the ionizable groups that contribute to the different hypoxanthine ionization steps in the main tautomers have been established. These and other related results are presented and discussed. Finally, the confidence developed in the predicted tautomeric populations in a modeled-ideal aqueous solution allows us to propose that the methodology applied here can be used for the study of prototropic tautomerism in heterocycles belonging to this class, particularly when the experimental work is challenging in both performance and physicochemical data analysis.     

Sufficiency and fuzziness in random experiments

In previous papers, the consequences of the “presence of fuzziness” in the experimental information on which statistical inferences are based were discussed. Thus, the intuitive assertion «fuzziness entails a loss of information» was formalized, by comparing the information in the “exact case” with that in the “fuzzy case”. This comparison was carried out through different criteria to compare experiments (in particular, that based on the “pattern” one, Blackwell's sufficiency criterion). Our purpose now is slightly different, in the sense that we try to compare two “fuzzy cases”. More precisely, the question we are interested in is the following: how will different “degrees of fuzziness” in the experimental information affect the sufficiency? In this paper, a study of this question is carried out by constructing an alternative criterion (equivalent to sufficiency under comparability conditions), but whose interpretation is more intuitive in the fuzzy case. The study is first developed for Bernoulli experiments, and the coherence with the axiomatic requirements for measures of fuzziness is also analyzed in such a situation. Then it is generalized to other random experiments and a simple example is examined.     

Stark broadening of neutral helium lines and spectroscopic diagnostics of pulsed helium plasma

Stark broadening parameters (widths and shifts) of two He I isolated spectral lines are measured in a plasma of a low-pressure pulsed arc. Plasma electron densities, determined by spectroscopic method based on previously calibrated He I lines, ranges from 1 x 10¹⁶ cm^-3 to 6 x 10¹⁶ cm^-3. The plasma electron temperature acquired by a Boltzmann plot of several He I lines, lies in the interval 8 000-30 000 K. Results of this work are compared with theoretical predictions and with other experimental data.Received: 30 April 2003, Published online: 29 July 2003PACS: 52.70.-m Plasma diagnostic techniques and instrumentation - 52.70.Kz Optical (ultraviolet, visible, infrared) measurements - 32.70.Jz Line shapes, widths, and shiftsR. Santamarta: Present address: DESY/ZEUS Hamburg, Germany.