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.     

Gas chromatography/combustion/isotope-ratio-monitoring mass spectrometric analysis of methylboronic derivatives of monosaccharides: a new method for determining natural 13C abundances of carbohydrates

Monosaccharides were derivatized using methylboronic acid and N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA), and the delta13C values of these derivatives measured by gas chromatography/combustion/isotope-ratio-monitoring mass spectrometry to determine the original 13C-content of the monosaccharides. Comparison with the measured off-line delta13 values of the monosaccharides shows that no fractionation in 13C takes place during derivatization. The methylboronic derivatization method has proven to be a new method for natural abundance isotopic analysis of intact monosaccharides (arabinose, xylose, fucose, fructose and glucose). The method is rapid, does not involve isotopic fractionation during derivatization, and gives more precise delta13C values than other methods reported. The method was successfully applied to determine the delta13C value of glucose of the freshwater alga Scenedesmus communis.     

The determination of coal combustion kinetics with thermogravimetry

This investigation concerns the determination of the kinetics of coal combustion. It is not well possible to use an exact analytical formula for the rate equation. For that reason a stepwise method is proposed, giving the activation energy as function of the reaction parameter , without assumption of any specific rate equation.

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Zusammenfassung Diese Arbeit beschäftigt sich mit der Kinetik der Kohleverbrennung. Für die Reaktionsgeschwindigkeit ist es jedoch nicht möglich, eine exakte analytische Gleichung anzuwenden. Aus diesem Grunde wird ein schrittweises Vorgehen vorgeschlagen, das die Aktivierungsenergie ohne Voraussetzung jeglicher spezifischer Geschwindigkeitsgleichungen als Funktion des Reaktionsparameters liefert.

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The authors wish to thank Mr. L. J. M. van der Valk for doing a lot of the experiments and Mr J. J. B. van, Hoist for making the drawings.     

Aminosulf(ox)ides as ligands for Iridium(I)-catalyzed asymmetric transfer hydrogenation

A new class of efficient catalysts was developed for the asymmetric transfer hydrogenation of unsymmetrical ketones. A series of chiral N,S-chelates (6-22) was synthesized to serve as ligands in the iridium(I)-catalyzed reduction of ketones. Both formic acid and 2-propanol proved to be suitable as hydrogen donors. Sulfoxidation of an (R)-cysteine-based aminosulfide provided a diastereomeric ligand family containing a chiral sulfur atom. The two chiral centers of these ligands showed a clear effect of chiral cooperativity. In addition, aminosulfides containing two asymmetric carbon atoms in the backbone were synthesized. Both the sulfoxide-containing beta-amino alcohols and the aminosulfides derived from 1,2-disubstituted amino alcohols gave rise to high reaction rates and moderate to excellent enantioselectivities in the reduction of various ketones. The enantioselective outcome of the reaction was favorably affected by selecting the most appropriate hydrogen donor. Enantioselectivities of up to 97% were reached in the reduction of aryl-alkyl ketones.     

Seasonal Variations in the Subsurface Ultraviolet‐B on an Inshore Pacific Coral Reef Ecosystem

Fringing coral reefs provide a unique opportunity to study shallow aquatic ecosystems. A fringing coral reef system located in close proximity to a developed region was considered in this study. In such an environment, the rate of decay of dissolved organic matter is high and the penetration of higher energy ultraviolet‐B (UVB) extends a greater influence on species diversity, particularly upon shallow benthic communities. Results from a 9 month subsurface UVB exposure measurement campaign performed at a site located on the southern Queensland coast (Hervey Bay, 25°S) are presented in this research. For this, a novel dosimetric technique was utilized to measure long‐term subsurface UVB exposures. The resultant data set includes exposure measurements made during the significant La Niña event of late 2010 which resulted in unprecedented high sea surface temperatures and severe flooding across eastern Australia, impacting upon the lagoon regions of the Great Barrier Reef and Queensland's southern estuaries, including the study site. The influence of season, diurnal tidal variation, cloud cover and solar zenith angle were analyzed over the campaign period. Mean minimum daylight water depth was found to be the most significant factor influencing subsurface UVB.