New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

Intercalation of Benzamide into Kaolinite

Well-crystallized kaolinite (K) was initially reacted at 60 degrees C with a water/dimethylsulfoxide (DMSO) mixture and the resulting intercalation derivative (K-DMSO) was characterized by powder X-ray diffractometry (PXRD), thermal analysis (simultaneous TG and DSC), and Fourier-transformed infrared spectroscopy (FTIR). Benzamide crystals were then melted with the K-DMSO derivative at 140 degrees C for 4 days, when a gradual displacement of DMSO by benzamide was observed within the interlayer spacing of the modified kaolinite. The resulting material, after extensive washing with acetone, was characterized and compared to the results obtained previously for the K-DMSO composite. Benzamide intercalation proceeded by gradual displacement of DMSO molecules until completion. The structural stabilization of the K-BZ derivative was explained through the establishment of hydrogen bonds between the carbonyl oxygen atoms of the intercalated benzamide and aluminol groups present at the surface of the kaolinite layer. The interlamellar spacing of K-BZ was shown to be possibly occupied by benzamide molecules that were located at a 68 degrees orientation in relation to the layer surface. Unlike most intercalation molecules such as DMSO, variations in the interplanar spacing of kaolinite were consistent with the nonkeying of any other part of the molecule between the aluminosilicate interlayers. Copyright 2000 Academic Press.     

Higher Hopf formulae for homology via Galois Theory

We use Janelidze's Categorical Galois Theory to extend Brown and Ellis's higher Hopf formulae for homology of groups to arbitrary semi-abelian monadic categories. Given such a category A and a chosen Birkhoff subcategory B of A, thus we describe the Barr-Beck derived functors of the reflector of A onto B in terms of centralization of higher extensions. In case A is the category Gp of all groups and B is the category Ab of all abelian groups, this yields a new proof for Brown and Ellis's formulae. We also give explicit formulae in the cases of groups vs. k-nilpotent groups, groups vs. k-solvable groups and precrossed modules vs. crossed modules.     

Determination of Henry''s law coefficients by combination of the equilibrium partitioning in closed systems and solid-phase microextraction techniques

This paper describes the determination of Henry's law coefficients by means of the EPICS (equilibrium partitioning in closed systems) technique in combination with SPME (solid-phase microextraction). The use of solid-phase microextraction-sampling allowed us to extend the possibilities of the equilibrium partitioning in closed systems technique with respect to the range of Henry's law coefficients which can be measured. Whereas the equilibrium partitioning in closed systems technique is limited to determine air–water equilibrium partitioning of volatile compounds with Henry's law coefficients of at least 0.06 (dimensionless), the current method allowed to measure coefficients between 0.0023 and 13.5. In this way Henry's law coefficients of 20 compounds, being in a range covering five orders of magnitude, were measured with relative standard deviations between 1.0 and 19.8% (mean standard deviation: 5.7%; median of standard deviations: 4.8%, n=99). Several types of compounds were examined i.e. aliphatic hydrocarbons, monocyclic and polycyclic aromatic hydrocarbons, chlorinated and fluorinated compounds, ethers and esters, biphenyl and N-containing compounds, including compounds for which availability of experimental Henry's law coefficients is limited. Measurement of the equilibrium partitioning in the 2 to 25°C range allowed to establish relations of Henry's law coefficient as a function of temperature.     

Characterisation of human hair surfaces by means of static ToF-SIMS: A comparison between Ga and C60 primary ions

This study deals with the secondary ion yield improvement induced by using C₆₀⁺ primary ions instead of Ga⁺ ones to characterize human hair surfaces by ToF-SIMS. For that purpose, a bunch of hair fibres has been analysed with both ion sources. A high improvement is observed for the detection of amino acids with C₆₀⁺ primary ions as compared to Ga⁺ ions. As an example, a yield enhancement factor greater than 3000 is found for the CNO⁻ peak. A similar gain is observed for the positive secondary ions characteristic of the amino acids. Most of the atomic ions, such as Ca⁺, O⁻ and S⁻, constitute minor peaks with C₆₀⁺ ions while they often dominate the spectrum in the case of Ga⁺ ions. However, with the C₆₀⁺ source, a series of inorganic combination peaks with the elements Ca, S and O are observed in the positive spectra (i.e. HCaSO₄⁺), while they are marginal with the Ga⁺ source. For the mass range beyond 100 m/z and in both polarities, the hair fingerprints are similar with both sources. In average, for a comparable number of primary ions per spectrum, the C₆₀⁺ ion source gives intensities between two and three orders of magnitude higher than the Ga⁺ one.