Highly selective hydroformylation of the cinchona alkaloids

The four naturally occurring cinchona alkaloids were subjected to hydroformylation to create an extra functional group that allows immobilization. Cinchonidine, quinine, and quinidine, could be hydroformylated with virtually complete terminal selectivity, using a rhodium/tetraphosphite catalyst. The cinchonidine aldehyde was reduced to the alcohol and subjected to reductive amination with benzylamine.     

Liquid chromatographic analysis of cinchona alkaloids in beverages

A method for the determination of Cinchona extract (whose main components are the alkaloids cinchonine, cinchonidine, quinidine, and quinine) in beverages by liquid chromatography was developed. A beverage with an alcohol content of more than 10% was loaded onto an OASIS HLB solid-phase extraction cartridge, after it was adjusted to pH 10 with 28% ammonium hydroxide. Other beverages were centrifuged at 4000 rpm for 5 min, and the supernatant was loaded onto the cartridge. The cartridge was washed with water followed by 15% methanol, and the Cinchona alkaloids were eluted with methanol. The Cinchona alkaloids in the eluate were chromatographed on an L-column ODS (4.6 mm id x 150 mm) with methanol and 20 mmol/L potassium dihydrogen phosphate (3 + 7) as the mobile phase. Cinchona alkaloids were monitored with an ultraviolet (UV) detector at 230 nm, and with a fluorescence detector at 405 nm for cinchonine and cinchonidine and 450 nm for quinidine and quinine (excitation at 235 nm). The calibration curves for Cinchona alkaloids with the UV detector showed good linearity in the range of 2-400 microg/mL. The detection limit of each Cinchona alkaloid, taken to be the concentration at which the absorption spectrum could be identified, was 2 microg/mL. The recovery of Cinchona alkaloids added at a level of 100 microg/g to various kinds of beverages was 87.6-96.5%, and the coefficients of variation were less than 3.3%. A number of beverage samples, some labeled to contain bitter substances, were analyzed by the proposed method. Quinine was detected in 2 samples of carbonated beverage.     

Microdetermination of cinchona alkaloids by atomic absorption spectroscopy

A sensitive and rapid microdetermination method has been developed for the determination of cinchona alkaloids via their mercury complex. Different parameters of the procedure have been thoroughly studied. The percentage recoveries for quinine, quinidine, cinchonine and cinchonidine were found to be 98.97 ±0.62, 99.06 ± 0.62, 98.90 ± 0.74, respectively. The results obtained are favourably compared to the official ones. The method is characterised by its specificity, accuracy and good precision.     

Absolute configuration and conformational features of alkaloids of the nitramine group and their derivatives

The absolute configurations of the asymmetric centers in the natural alkaloids nitramine (6R,7eS), isonitramine (6S, 7eS), and sibirine (6R,7eR) have been established by the circular dichroism method using the octant rule.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 727–730, November–December, 1986.     

Absolute configuration and conformational features of alkaloids of the nitramine group and their derivatives

The absolute configurations of the asymmetric centers in the natural alkaloids nitramine (6R,7eS), isonitramine (6S, 7eS), and sibirine (6R,7eR) have been established by the circular dichroism method using the octant rule.     

Highly tunable arylated cinchona alkaloids as bifunctional catalysts

We report the design and evaluation of a library of chiral bifunctional organocatalysts in which the distance between the catalytically active units can be systematically varied.     

Ion-pair extraction of some cinchona alkaloids with various chiral organic anions

Some cinchona alkaloids, the quinine/quinidine and cinchonine/cinchonidine pairs, are extracted by ion-pair formation with some chiral amino acids and d-camphorsulfonic acid. Their extraction behaviors are examined and the differences between the two isomers are compared. These alkaloids are extracted into chloroform in the pH range 4–7 as the 1:1 ion-pair with the organic acid. The relationship between the distribution ratio of the ion-pair and pH is discussed. In the pH range between the pK_a1 and pK_a2 values of these alkaloids, logarithmic plots of the distribution ratio are independent of pH. In this pH region, the extraction constants are determined and the differences caused by the ion-pair formation are discussed.     

Binding behaviour and solubilisation of p-sulfonatocalixarenes to cinchona alkaloids

In this study, we investigated the binding behaviours of three water-soluble p-sulfonatocalixarenes with four cinchona alkaloids in aqueous and phosphate buffer solutions (pH 7.2 and 2.0). The complexation stability constants obtained by fluorescence titrations were comparatively discussed from several aspects: host cavity, pH effect and ionic strength. Among three hosts, p-sulfonatocalix[4]arene (SC4A) forms the most stable complexes with cinchona alkaloids, especially in acidic aqueous conditions. Furthermore, SC4A was elected as model drug carrier for cinchona alkaloids, where solubilisation by the complexation of SC4A and mimic release from the calixarene cavity in the presence of negatively charged micelles were initially studied.     

New results on the mass spectra of cinchona alkaloids

The electrospray ionization (ESI) mass spectra of 16 cinchona alkaloid compounds were studied for the first time. The electron ionization (EI) spectra of 22 cinchona alkaloids were also recorded, 14 of which had not been examined previously. In the case of EI the characteristic direction of the fragmentation is the scission of the C8-C9 bond. Under EI the cleavage of the C4'-C9 bond occurs only in the case of hydrogenated cinchona alkaloids, whereas the C9-O bond cleavage can be observed in the case of ester and ether derivatives. At a low capillary exit voltage (CapEx) in the ESI measurements there is no fragmentation, and only the [M + H](+) and in some cases the double protonated [M + 2H](2+) ions can be detected. On increasing the CapEx the characteristic primary direction is the cleavage of the C9-O bond, which was observed in the case of epialkaloids and esterified or etherified cinchona derivatives, respectively. Copyright 2000 John Wiley & Sons, Ltd.     

Absolute configuration of sebiferine

Absolute configuration of sebiferine has been determined.     

Enantioselective nitroaldol reaction of alpha-ketoesters catalyzed by cinchona alkaloids

The development of highly enantioselective and general catalytic nitroaldol (Henry) reactions with ketones is a challenging yet desirable task in organic synthesis. In this communication, we report an asymmetric nitroaldol reaction with alpha-ketoesters catalyzed by a new C6'-OH cinchona alkaloid catalyst. This is the first highly efficient organocatalytic asymmetric Henry reaction with ketones. This reaction is operationally simple and affords high enantioselectivity as well as good to excellent yield for a broad range of alpha-ketoesters.     

Absolute configuration of fucoxanthin

The common natural isomer of the allenic carotenoid fucoxanthin has the 3S,5R,6S,3′S,5′R,6′R configuration.