Stereoselective Rh-catalyzed hydrogenation of cyclobutyl chiral enamides: double stereodifferentiation vs catalyst-controlled diastereoselection

The hydrogenation reactions of several cyclobutyl enamides derived from (-)-alpha-pinene or (-)-verbenone have been investigated by using different catalysts. The chiralities of both the substrate and the catalyst as well as the Z/E stereochemistry of the double bond have been considered, and the observed diastereoselectivity has been rationalized. For enamides with the double bond separated from the cyclobutane by a methylene, the Wilkinson catalyst did not induce any diastereoselection, but excellent diastereoselectivity was observed when using Et-DuPHOS-Rh and ChiraPHOS-Rh. The configuration of the new stereogenic center was catalyst-dependent and can be rationalized according to the Halpern mechanism. For (Z)-enamides with the double bond directly linked to the cyclobutane ring, the chirality of the substrate governed the diastereoselection and the Halpern mechanism seemed not to be operative in the hydrogenation with ChiraPHOS, with the configuration of the new stereogenic center being determined by steric effects. On the contrary, the chirality of the catalyst was the factor determining the stereochemistry of the major products with alkyl-DuPHOS-Rh. Z/E stereochemistry influenced the stereodifferentiation, and a different behavior for each Z or E stereoisomer was found. For both (Z)- and (E)-enamides, some instances of match/mismatch between the chirality of the substrate and that of the catalyst were observed. As a result of all of these studies, a series of new cyclobutyl alpha-amino acids has been synthesized. These products are interesting to incorporate into conformationally constrained peptides.     

Isotachophoretic determination of stability constants of Ho and Y complexes with diethylenetriaminepentaacetic acid and 1,4,7,10-tetraazadodecane-N,N',N'',N'''-tetraacetic acid

The method of capillary isotachophoresis with conductivity detection was applied for the determination of the physico-chemical characteristics (conditional stability constants log beta') of holmium and yttrium complexes with DTPA (diethylenetriaminepentaacetic acid) and DOTA (1,4,7,10-tetraazadodecane-N,N',N',N'-tetraacetic acid). The log beta' determination is based on the linear relation between the stability constants of lanthanide-DTPA (lanthanide-DOTA) complexes and the reduction of the zone of the complex owing to the bleeding phenomena (liberating free metal ion). The stability constants calculated using this relationship are comparable with the literary data obtained by other methods for both holmium (log beta'(Ho-DTPA)=21.9, log beta'(Ho-DOTA)=24.5) and yttrium complexes (log beta'(Y-DTPA)=21.2, log beta'(Y-DOTA)=24.4). Capillary isotachophoresis was applied for the determination of the optimum composition of the reaction mixture (metal:ligand ratio) as well.     

Conformational dynamics of a bispyridinium cyclophane

A complete study of the conformational behavior of 4,8-diaza-3(1,4),9(4,1)-dipyridina-1,6(1,4)-dibenzenacyclodecaphan-3(1),9(1)-bis(ilium) bishexafluorophosphate is described. This study allows us to conclude that the process observed by which the different chemical shifts of the pyridinium protons show coalescence at a high-temperature 1H NMR is the rotation around the C-N bond, whereas the conformational equilibrium between the four conformers is produced at low temperature.     

Trace analysis of lead by anodic stripping voltammetry with collection at interdigitated microelectrodes in small-volume samples

A simple and sensitive electroanalytical method was developed for microvolume trace elements determination. Commercially available interdigitated microelectrodes (IDA) from ALS Japan Inc. based on a thin carbon film technology were used. Anodic stripping voltammetry with collection at IDA was applied. Carbon IDA microbands were coated with a pre-deposited mercury film for better performance. The method with this sensor enables analysis of some heavy metals in total sample volumes as small as 0.05 cm³. The method was applied to Pb in blood samples determination by a standard addition method.     

Influence of biomass on hydrodynamics of an internal loop airlift reactor

The effect of the biomass presence on the overall circulation velocity, the linear velocities both in the riser and the downcomer and the overall gas hold-up was studied in a three-phase internal loop airlift reactor (ILALR). The measured data were compared with those obtained using a two-phase system (air—water). All experiments were carried out in a 40 dm³ ILALR at six different biomass concentrations (ranging from 0 g dm⁻³ to 7.5 g dm⁻³), at a temperature of 30°C, under atmospheric pressure. Air and water were used as the gas and liquid model media, respectively. Pellets of Aspergillus niger produced during the fermentation of glucose to gluconic acid in the ILALR were considered solid phase. In addition, liquid velocities were measured during the fermentation of glucose to gluconic acid using Aspergillus niger. All measurements were performed in a bubble circulation regime. At given experimental conditions the effect of the biomass on the circulation velocities in the ILALR was negligible. However, increasing of the biomass concentration led to lower values of the total gas hold-up. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

Selective hydrogenations of steroids catalyzed by heterogenized Ru complexes

Summary [RuCl₂(PPh₃)₃], [{RuCl₂(TPPMS)₂}₂] and their heterogenized analogs were applied in the selective hydrogenation of 17-keto- and α,β-unsaturated ketosteroids. In basic conditions these complexes selectively hydrogenated the C=O bonds, similarly to the results obtained in the case of α,β-unsaturated aldehydes. A new method was developed for the synthesis of an expensive steroid alcohol, which can be prepared traditionally in a more complicated way.     

Evaluating the significance threshold in robustness testing. A critical discussion on the influence of time in molecular fluorescence spectrometry

Robustness experiments are performed in analytical chemistry to assess the behaviour of an analytical procedure under conditions slightly different from those of the experimental optimum. This work presents a study of robustness applied to a previously proposed fluorescent methodology using two replicated 2(7-4) saturated fractional factorial designs. A comparison is established between three different ways to test the significance of the effects of the variables involved on the response signal. Critical discussions about the most appropriate threshold to be introduced when testing for significance of the factors and the influence of the time necessary to carry out the experiments are included.     

Study of Ligand Substitution Reactions at Pentacyanoferrates(II) in Aqueous Salt and Micellar Solutions

The ligand substitution reactions Fe(CN)(5)(4-(t)bupy)(3-) + 4-CNpy and Fe(CN)(5)(4-(t)bupy)(3-) + pzCO(2)(-) (4-(t)Bupy = 4-tert-butylpyridine; 4-CNpy = 4-cyanopyridine; pzCO(2)(-) = pyrazinecarboxylate) were studied in several aqueous salt and micellar solutions. Kinetic data in aqueous solutions showed that the two processes follow a dissociative mechanism, D, and the dependence of the first-order rate constants on [salt] on electrolyte aqueous solutions allow the estimation of the activation volumes corresponding to both reactions. Under true first-order conditions no kinetic micellar effects were found in anionic (SDS) and nonionic (Triton X-100) aqueous micellar solutions. In cationic micellar solutions (CTAB, CTAC, and TTAB) small kinetic micellar effects were found. These were related to the different ionic concentrations and the different polarity and structure of the Stern layer surrounding the cationic micellar aggregates, where the reactions take place, with respect to pure water. Copyright 2000 Academic Press.     

Saturated heterocycles, 162 [1]. synthesis and steric structures of 3,4-disubstituted 1,6,7,11b-tetrahydropyrimido[6,1-a]isoquinolin-2-ones

The reaction of 1-(hydrazidomethyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline 3 with aromatic aldehydes yield hydrazones 4a,b or pyrimido[6,1-a]isoquinolines 5a-c depending upon the proportions of the reagents. With ketones, 3 gives only hydrazones 4a-d and 7 , which can be transformed to pyrimidoisoquinolines 10a-e and 11 with aldehydes. The ring closures are stereospecific; the relative configurations were determined by DNOE measurements.     

A non local density functional calculation of the diamagnetic susceptibilities and other electronic properties of noble gases and closed-shell ions

The non local weighted-density approximation (WDA) to the exchange-correlation potentialV _xc (r) is used to compute electron densities, ionization potentials and electron affinities of several atoms and ions. Especial care is taken in calculating and discussing 〈r ²〉 in noble gas atoms. Good results are obtained for all those quantities, but it is critical that the WDA is applied in such a way that it preserves the correct larger behaviour ofV _xc (r). A comparison of the calculated electron density with that of the Hartree-Fock method shows the effects of coulomb correlation. The density rearrangements upon the introduction of correlation agree qualitatively with the results of Configuration-Interaction calculations