Efficient enantiomeric synthesis of pyrrolidine and piperidine alkaloids from tobacco

An enantiomeric synthesis of six piperidine and pyrrolidine alkaloids, (S)-nornicotine 1, (S)-nicotine 2, (S)-anatabine 3, (S)-N-methylanatabine 4, (S)-anabasine 5, and (S)-N-methylanabasine 6, known as natural products in tobacco, was established from a common chiral homoallylic (S)-3-(1-azido-but-3-enyl)-pyridine 15. An intramolecular hydroboration-cycloalkylation of the homoallylic azide intermediate 15 served as the key step in the pyrrolidine ring formation. A ring closing metathesis reaction (RCM) of a diethylenic amine intermediate (S)-allyl-(1-pyridin-3-yl-but-3-enyl)-carbamic acid benzyl ester 20 served as the key step in the piperidine ring formation. From the commercially available 3-pyridinecarboxaldehyde 13, a short and convenient enantiomeric synthesis of tobacco alkaloids is described: (S)-nornicotine 1 (5 steps, with an overall yield of 70%), (S)-nicotine 2 (6 steps, 65%), (S)-anatabine 3 (8 steps, 30%), (S)-N-methylanatabine 4 (8 steps, 25%), (S)-anabasine 5 (8 steps, 35%), and (S)-N-methylanabasine 6 (8 steps, 25%).     

A flavonoid bioside ofOxytropis strobilaceae

Chemistry of Natural Compounds -     

Integrated Systems for Water Cleavage by Visible Light; Sensitization of TiO2 Particles by Surface Derivatization with Ruthenium Complexes

Irradiation of acidic (pH 2) solutions of RuL₃²⁺ 2Cl^? (L = diisopropyl 2,2′-bipyridine-4,4′ -dicarboxylate) in the presence of TiO₂ at 100°C leads to the loss of one bipyridyl ligand and the chemical fixation of RuL₂ at the surface of teh TiO₂ particles through formation of Ru-O-Ti bonds. These surface complexes are very stable and shift the absorption onset of TiO₂ beyond 600 mm. Efficient sensitization H₂-generation is achieved with this system beginning in the wave length domain between 590 and 665 nm. Preliminary water cleavage experiments with bifunctional TiO₂/Pt/RuO₂ redox catalyst are reported.     

Castelnuovo–Mumford Regularity of Associated Graded Modules and Fiber Cones of Filtered Modules

We give bounds on the Castelnuovo–Mumford regularity of the associated graded module of an arbitrary good filtration and of its fiber cone. These bounds extend previous results of Rossi–Trung–Valla and Linh.     

Efficient and green synthesis of 4H-pyran derivatives under ultrasound irradiation in the presence of K2CO3 supported on acidic montmorillonite

Acid-treated montmorillonite coating with K₂CO₃ is used as a catalyst for an efficient, rapid, one-pot synthesis of 4H-pyran derivatives in good yield under ultrasonic irradiation. The catalyst is environmentally benign, easy handling, nontoxic, stable in air, and inexpensive.     

New class of chiral ligands derived from isosorbide: first application in asymmetric transfer hydrogenation

A new class of β-amino alcohol and diamine ligands was prepared from isosorbide as a chiral renewable resource. The original wedge-shaped structure of isosorbide offers an interesting chiral pocket to promote the metal-catalyzed enantioselective reduction of ketones by transfer hydrogenation.     

Use of evaporative light scattering detector in the detection and quantification of enantiomeric mixtures by HPLC

Routinely used in our laboratories at analytical scale, an evaporative light scattering detector (ELSD) has proved to be versatile in the detection of enantiomeric resolution using chiral stationary phases by HPLC. Though this kind of detector has been widely used in various domains, its application in enantiomeric resolution has not been discussed in the literature and is found to have very specific features especially in the quantitative perspective. In contrast with the UV detection, the peak area from ELSD for both enantiomers of a racemic mixture may not be the same. This complicates the assessment of the enantiomeric purity of unknown samples. This current work deals with some practical aspects in the detection of enantiomers and in accurate quantitative determination of enantiomeric purity by ELSD. Effects of analyte nature (more precisely molecular weight and volatility), peak shape and peak shape difference between enantiomers on the quantitative integration by ELSD are discussed in connection with the UV-detection results. The calibration for quantitative enantiomeric analysis and its effectiveness are demonstrated.     

Characterization and phytoremediation of abandoned contaminated mining area in Portugal by INAA

This study aims to find out a vascular plant species that accumulate relatively high concentrations of arsenic (As) for its use as phytoremediator at abandoned and contaminated mining areas, such as São Domingos mines (Portugal). The assessment of As contamination levels in soils and plants of other similar sites in the north of the country (Castromil and Poço de Freitas) was also conducted; and the sample analyses were made by instrumental neutron activation analysis. Agrostis genera have shown higher As transfer coefficients than other studied plant species and, in particular, Agrostis curtisii has shown a reasonable ability to accumulate high concentration of this toxic element.     

Synthesis of functionalized chiral ammonium,imidazolium, and pyridinium-based ionic liquids derived from (−)-ephedrine using solvent-free microwave activation. Applications for the asymmetric Michael addition

An efficient procedure for the synthesis of functionalized chiral ammonium, imidazolium, and pyridinium-based ionic liquids derived from (1R, 2S)-ephedrine using solvent-free microwave activation has been described. Good yields were obtained in very short reaction time. These chiral ionic liquids were used as chiral reaction media for the asymmetric Michael addition, giving good yields and moderate enantioselectivities.     

Casimir force on amplifying bodies

Based on a unified approach to macroscopic QED that allows for the inclusion of amplification in a limited space and frequency range, we study the Casimir force as a Lorentz force on an arbitrary partially amplifying system of linearly locally responding (isotropic) magnetoelectric bodies. We demonstrate that the force on a weakly polarisable/magnetisable amplifying object in the presence of a purely absorbing environment can be expressed as a sum over the Casimir-Polder forces on the excited atoms inside the body. As an example, the resonant force between a plate consisting of a dilute gas of excited atoms and a perfect mirror is calculated.