Chiral squaramide derivatives are excellent hydrogen bond donor catalysts

Thioureas represent the dominant platform for hydrogen bond promoted asymmetric catalysts. A large number of reactions, reported in scores of publications, have been successfully promoted by chiral thioureas. The present paper reports the use of squaramides as a highly effective new scaffold for the development of chiral hydrogen bond donor catalysts. Squaramide catalysts are very simple to prepare. The (-)-cinchonine modified squaramide (5), easily prepared through a two-step process from methyl squarate, was shown to be an effective catalyst, even at catalyst loadings as low as 0.1 mol%, for the conjugate addition reactions of 1,3-dicarbonyl compounds to beta-nitrostyrenes. The addition products were obtained in high yields and excellent enantioselectivities.     

Simple chiral diene ligands provide high enantioselectivities in transition-metal-catalyzed conjugate addition reactions

Chiral dienes possessing the bicyclo[2.2.2]octadiene framework were prepared readily through the [4 + 2] cycloaddition of ( R)-alpha-phellandrene with methyl propiolate as the key step. Diene 9, substituted with a tertiary alcohol on one of the two double bonds, is prepared in just one step from the cycloadduct and is highly effective as a chiral ligand for rhodium-catalyzed asymmetric conjugate addition reactions, giving the corresponding addition products with higher enantioselectivity than other chiral dienes.     

Nanocellulose characteristics from the inner and outer layer of banana pseudo-stem prepared by TEMPO-mediated oxidation

Many tonnes of agricultural wastes are generated annually, which contains a relatively high amount of cellulose; banana pseudo-stem is one waste type that is a promising material for nanocellulose production. This research characterised nanocellulose from inner and outer layers of banana pseudo-stem as a preliminary research strategy for designing biodegradable packaging material from banana pseudo-stem nanocellulose. Nanocellulose was successfully prepared through TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl)-mediated oxidation. The extracted nanocellulose from both the inner and outer layers had observed widths of approximately 7–35 nm and long fibrillated fibre. They had high negative zeta potential (lower than ?33.6) that provided good colloidal stability. The purity of the nanocellulose was high as demonstrated by ¹³C solid-state NMR and Fourier transform infrared spectroscopy. Nanocellulose from both layers was significantly more crystalline than the raw materials. Thermal stability of nanocellulose sourced from inner and outer layers was relatively similar, with degradation temperature of approximately 220 °C, which was slightly lower than the degradation temperature of its native form (232 °C for inner layer and 261 °C for outer layer).     

Unexpected regioselective debenzylation leading to modification of both rims of α-cyclodextrin

Diisobutylaluminum hydride-mediated debenzylation of perbenzylated α-cyclodextrin was investigated using modified conditions. It was found that the reaction proceeded much slower to allow a more controlled removal of benzyl groups. Prolonged reaction time led to the unprecedented observation that a cleavage of up to two benzyl groups can occur at the secondary rim in a highly regioselective manner.     

High quality beam shaping by square soft-edge diaphragm combined with liquid crystal spatial light modulator

<正>The square soft-edge diaphragm with round angle is designed by Matlab,and is sent to a liquid crystal spatial light modulator by the computer.In order to obtain precompensation for the following laser system, local diaphragm transmission can be adjusted by feedback signals of surface-channel charge-coupled device (SCCD).This method can reduce the diffraction effect and realize no modulation,high stability,high homogeneity,and large scale laser beam.Several parameters of soft-edge diaphragms which affect the laser beam quality are studied systematically,and the optimized values are obtained.The method can avoid the serious modulation of hard edges and provide soft-edge diaphragms of different shapes in a fast and convenient way for the large scale laser beam system.     

Determination of sulfite with emphasis on biosensing methods: a review

Sulfite is used as a preservative in a variety of food and pharmaceutical industries to inhibit enzymatic and nonenzymatic browning and in brewing industries as an antibacterial and antioxidizing agent. Convenient and reproducible analytical methods employing sulfite oxidase are an attractive alternative to conventional detection methods. Sulfite biosensors are based on measurement of either O₂ or electrons generated from splitting of H₂O₂ or heat released during oxidation of sulfite by immobilized sulfite oxidase. Sulfite biosensors can be grouped into 12 classes. They work optimally within 2 to 900 s, between pH 6.5 and 9.0, 25 and 40 °C, and in the range from 0 to 50,000 μM, with detection limit between 0.2 and 200 μM. Sulfite biosensors measure sulfite in food, beverages, and water and can be reused 100–300 times over a period of 1–240 days. The review presents the principles, merits, and demerits of various analytical methods for determination of sulfite, with special emphasis on sulfite biosensors.     

Stereocontrolled synthesis of 20,21-dihydro N-methylwelwitindolinone B isothiocyanate

Described is a concise synthesis of the 20,21-dihydro analog of N-methylwelwitindolinone B isothiocyanate, wherein a cationic homoallyl to cyclopropylmethyl rearrangement is circumvented by hydrogenation of the offending double bond.     

Total synthesis of N-methylwelwitindolinone D isonitrile

Described is a concise total synthesis of N-methylwelwitindolinone D isonitrile, the first in a family of complex bicyclo[4.3.1]decane-containing indole alkaloids to yield to synthesis. The complete carbon core of the natural product was assembled rapidly through a Lewis acid-mediated alkylative coupling followed directly by a palladium-catalyzed enolate arylation reaction. The final ring of the pentacycle was introduced by an indole oxidation/cyclization, and the isonitrile was installed through the rearrangement of an aldehyde to an isothiocyanate followed by desulfurization.     

New method for chloroamidation of olefins. Application in the synthesis of N-glycopeptides and anticancer agents

Chloroamidation of olefins using a new reagent system (COCl)2-AgNO3-CH3CN was observed. Various glycals with this reagent system produce 2-chloro-1-acetamido sugars in good yields which, in turn, were converted to free amino derivatives and various glycopeptides. The acetamido sugar derivatives and free amines were found to be promising anticancer agents against the U-87 malignant glyoma (a brain tumor) cell line with IC-50=1 nm-22 microM, and they were found to be far less cytotoxic against a normal human embryonic kidney cell line.