Diastereoselective hydroformylation of 2-substituted allylic o-DPPB-esters-on the origin of 1,2-asymmetric induction

2-Substituted secondary alcohol o-DPPB esters (o-DPPB=ortho-diphenylphosphanylbenzoyl) have been prepared and their o-DPPB-directed diastereoselective hydroformylation examined. It was found that the diastereoselectivity increased as a function of the steric demand of the substituents both at the stereogenic center and in the alkene 2-position. Hydrolytic cleavage of the o-DPPB group afforded-via the lactols 29-the corresponding lactones 30, the relative configurations of the vicinal stereogenic centers of which were ascertainable by 2D-NOESY spectroscopy. In addition, a crystal structure analysis of the hydroformylation product 2 d provided further confirmation of the relative configuration. Replacement of the ester carbonyl group of the o-DPPB by a methylene unit resulted in significantly worse diastereoselectivity in the course of the hydroformylation (34-->35), which indicates a decisive role for the ester carbonyl function. All the experimental observations were combined in a model of the origin of the 1,2-asymmetric induction during the title reaction. The key feature is the consideration of diastereomeric trigonal-bipyramidal rhodium-hydrido-olefin complexes I and II, capable on the basis of the Hammond postulate of acting as good models for the transition states of the selectivity-determining hydrometalation step. Investigation of these complexes by force-field methods indicated good correlation between theoretically predicted and experimentally determined diastereoselectivities.     

Synthesis of stereo-defined α-trifluoromethyl (Tfm)-malic units

Aldol reactions of titanium enolates of N-acyl-1,3-oxazolidin-2-ones with ethyl trifluoropyruvate occurred with low to good stereoselectivity depending on the steric properties of the N-acyl group. Attempts to transform the resulting aldols into peptidomimetics incorporating stereo-defined α-trifluoromethyl (Tfm)-malic units are described.     

Stabilization of p-block organoelement terminal hydroxides, thiols, and selenols requires newer synthetic strategies

Metal hydroxides represent a very interesting and highly useful class of compounds that have been known to chemists for a very long time. While alkali and alkaline earth metal hydroxides (s‐block) are commonplace chemicals in terms of their abundance and their use in a chemical laboratory as bases, the interest in Brønsted acidic molecular terminal hydroxides of p‐block elements, such as aluminum and silicon, has been of recent origin, with respect to the variety of applications these compounds can offer both in materials science and catalysis. Moreover, these systems are environmentally friendly, relative to the metal halides, owing to their ‐OH functionality (resembling that of water). Design and conceptualization of the corresponding terminal thiols, selenols, and tellurols (M? SH, M? SeH, and M? TeH) offer even more challenging problems to synthetic inorganic chemists. This concept summarizes some of the recent strategies developed to stabilize these otherwise very unstable species. The successful preparation of a number of silicon trihydroxides a few years back resulted in the generation of several model compounds for metal–silicates. The recent synthesis of unusual aluminum compounds such as RAl(OH)₂, RAl(SH)₂, and RAl(SeH)₂ with terminal EH (E=O, Se, or Se) groups is likely to change the ways in which some of the well‐known catalytic conversions are being carried out. The need for very flexible and innovative synthetic strategies to achieve these unusual compounds is emphasized in this concept.     

Simultaneous Spectrophotometric Determination of Group B Vitamins Using Parallel Factor Analysis: PARAFAC

In this work, a simple and rapid analytical procedure was applied for simultaneous determination of folic acid (vitamin B₀), thiamin (vitamin B₁), riboflavin (vitamin B₂) and pyridoxal (vitamin B₆) based on the absorbance data in the pH range 2.0‐12.0 at 25 °C using parallel factor analysis (PARAFAC). The effect of the pH as the most important factor on the sensitivity of the determination was studied. The spectral data were recorded in 400‐650 nm intervals and a 2‐12 pH range for all four vitamins. The calibration set was constructed in the concentration ranges of 4‐22, 1‐20, 6‐26, and 4‐20 μg mL^?;1 for B₆,B₂,B₁ and B₀, respectively. The root mean squares errors of prediction for the prediction set, (RMSEP), are 0.65, 0.63, 1.13 and 0.34 for B₀,B₁,B₂ and B₆, respectively. The recovery percent for the validation set are in the range of 90.6 to 107.0%. The effect of the experimental conditions and diverse species were discussed. The optimum values of these factors were searched according to the relative standard deviation of the prediction set of mixtures solutions.     

Neue acetonylsubstituierte Azole I. 5-Acetonyl-1,2,4-oxadiazole

Aliphatic amidoximesR—C (NH₂)=NOH react with diketene to yield 5-acetonyl-3-alkyl-1,2,4-oxadiazoles, which are susceptible to a wide variety of reactions at the keto-group as well as at the methylene-group. Their transformations into 1-methyl-2-oxadiazolyl-vinylN,N-dimethylcarbamates, 2-chloro-1-oxadiazolylpropenes, 1-oxadiazolyl-2-(1,2,4-triazol-1-yl)propenes, 1,1-dichloro-1-oxadiazolylacetones and 3-hydroxy-2-oxadiazolyl-crotonic amides are described as well as their reactions with diazonium salts, with sodium nitrite and with carbon disulfide. Further products obtained are carbamates of of 1-oxadiazolyl-2-oxo-propane-1-oximes, 2-chloro-2-oxadiazolylvinyl phosphates and an oxadiazolyl pyrimidine.

Herrn Prof. Dr.Klaus Weissermel zu seinem 60. Geburtstag.     

Approximate transferability in alkanenitriles

The atomic and bond properties of a series of alkanenitriles were calculated in order to analyze the transferability of the CN, methyl, and methylene groups. The calculations were carried out using the atoms in molecules (AIM) theory on RHF/6‐31++G**// RHF/6‐31G** wave functions obtained for compounds CN–R (R ranging from H to C₁₁H₂₃). Linear correlations between L(Ω) and N(Ω) were used to establish N(CH₂) and N(CH₃) nearly transferable values. Average values and maximum differences to the mean value of several properties were used for classifying the CN group. It shows a transferable behavior along the CN–R series for R>Et. The methyl group presents specific properties when R<Pr. The methylene groups can be classified considering both their position with respect to the end of the chain and the position with respect to the CN group. The atomic energy displays a dependence on the molecular size. Although this behavior does not allow to consider this property as transferable, both the ab initio total electronic molecular energies and the experimental heats of formation can be fitted, by linear regression analysis, as a function of the number of methylene groups. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Surface composition and property of film prepared with aqueous dispersion of polyurethaneurea-acrylate including fluorinated block copolymer

The aqueous dispersion of polyurethaneurea-acrylate (PUA) including small amount of fluorinated block copolymers containing carboxyl groups (PATF), which can be dissolved in water, was used to make films and the surface properties of these films were examined. The experimental data show that the modified PUA film exhibits a hydrophobic surface property, although the original surface of PUA film is hydrophilic. The surface composition of the modified PUA film was measured by ATR and XPS. The results indicate that there is a concentration gradient of the fluorine groups along the lines of thickness of the modified film and towards the outmost surface layer, resulting from the migration of fluorinated blocks to the air side surface of the modified PUA film during the film formation process. However, the PUA film can not be modified effectively by adding the sodium salt of PATF, since the urethane groups in the system are easy to occupy on the surface of the film.     

Protection of immobilized sulfhydryl groups against autooxidation by alterations in their microenvironment

Immobilized sulfhydryl groups were prepared by partial thiolation of NH₂-glass beads. The microenvironment of the immobilized SH groups was varied by different chemical modifications of neighboring NH₂ groups. Introduction of a strong charge in the surroundings of immobilized sulfhydryls results in their dramatic stabilization against autooxidation. This effect is due to the salting of O₂ from the surface microlayer of the thiolated beads.