Ruthenium-catalyzed reactions of 1-cyclopropyl-2-propyn-1-ols with anilines and water via allenylidene intermediates: selective preparation of tri- and tetrasubstituted conjugated enynes

Ruthenium-catalyzed efficient preparation of the conjugated enynes can be carried out in the reactions of 1-cyclopropyl-2-propyn-1-ols with nitrogen- and oxygen-centered nucleophiles such as anilines and water in the presence of a catalytic amount of sulfur-bridged diruthenium complexes. The use of such complexes as catalysts realizes the completely stereoselective preparation of tri- and tetrasubstituted conjugated enynes, where ruthenium-allenylidene complexes work as key intermediates. The direct attack of nucleophiles on a cyclopropane ring connected to an allenylidene ligand is a key step to obtain the enynes stereoselectively.     

Comprehensive separation of secondary metabolites in natural products by high-speed counter-current chromatography using a three-phase solvent system

High-speed counter-current chromatography (HSCCC) using the three-phase solvent system n-hexane-methyl acetate-acetonitrile-water at a volume ratio of 4:4:3:4 was applied to the comprehensive separation of secondary metabolites in several natural product extracts. A wide variety of secondary metabolites in each natural product was effectively extracted with the three-phase solvent system, and the filtered extract was directly submitted to the HSCCC separation using the same three-phase system. In the HSCCC profiles of crude natural drugs listed in the Japanese Pharmacopoeia, several physiologically active compounds were clearly separated from other components in the extracts. The HSCCC profiles of several tea products, each manufactured by a different process, clearly showed their compositional difference in main compounds such as catechins, caffeine, and pigments. These HSCCC profiles also provide useful information about hydrophobic diversity of whole components present in each natural product.     

New sensitive derivatization of hydroxysteroids for high-performance liquid chromatography with fluorescence detection

New highly sensitive and moderately reactive derivatization reagents for hydroxysteroids have been developed. Two derivatization reagents, 1-anthroyl nitrile and 9-anthroyl nitrile, were readily prepared from the corresponding anthracenecarboxylic acid in two steps. The hydroxysteroid was condensed with the anthroyl nitrile in the presence of triethylamine under mild conditions. The resulting ester showed a single peak of the theoretical shap on the chromatogram and provided excellent sensitivity. The detection limit of the C-21 ester formed from cortisol was 10 pg in normal-phase chromatorgraphy.     

Surface affinity chromatographic separation of blood cells. III. Effect of molecular weight of polyethylene glycol bonded stationary phases on elution behaviour of human blood cells

The chromatographic behaviour of human peripheral blood cells on four kinds of oxirane-coupled polyethylene glycol (PEG)--Sepharose 6B columns was investigated by using an eluent containing 2% of dextran T40. The retention volumes of lymphocytes, granulocytes and platelets at pH 7.5 have a strong dependence on the average molecular weight of the bonded PEG in the range 400-20,000, increasing with increasing molecular weight. Further, the same tendency for the retention behaviour was also observed at the isoelectric points determined for the four kinds of blood cells by using the cross-partition method. For lymphocytes and granulocytes hydrophobic interactions with the bonded PEG phase were found to be predominant, whereas for erythrocytes and platelets electrostatic interactions were also taken into account.     

Phenylselenenyl chloride as a reagent for the facile preparation of cyclic ethers from diolefins

Various cyclic ethers are prepared in good to excellent yields by treating diolefins with phenylselenyl chloride in aqueous acetonitrile. This is the most facile method for organoselenium-induced formation of cyclic ethers from diolefins so far reported.     

Catalytic cyclopropanation of alkenes via (2-furyl)carbene complexes from 1-benzoyl-cis-1-buten-3-yne with transition metal compounds

The reaction of alkenes with conjugated ene-yne-ketones, such as 1-benzoyl-2-ethynylcycloalkenes, with a catalytic amount of Cr(CO)(5)(THF) gave 5-phenyl-2-furylcyclopropane derivatives in good yields. The key intermediate of this cyclopropanation is a (2-furyl)carbene complex generated by a nucleophilic attack of carbonyl oxygen to an internal alkyne carbon in pi-alkyne complex or sigma-vinyl cationic complex. A wide range of late transition metal compounds, such as [RuCl(2)(CO)(3)](2), [RhCl(cod)](2), [Rh(OAc)(2)](2), PdCl(2), and PtCl(2), also catalyzes the cyclopropanation of alkenes with ene-yne-ketones effectively. When the reactions were carried out with dienes as a carbene acceptor, the more substituted or more electron-rich alkene moiety was selectively cyclopropanated with the (2-furyl)carbenoid intermediate.