Organocatalytic functionalization of carboxylic acids: isothiourea-catalyzed asymmetric intra- and intermolecular Michael addition--lactonizations

Tetramisole promotes the catalytic asymmetric intramolecular Michael addition-lactonization of a variety of enone acids, giving carbo- and heterocyclic products with high diastereo- and enantiocontrol (up to 99:1 dr, up to 99% ee) that are readily derivatized to afford functionalized indene and dihydrobenzofuran carboxylates. Chiral isothioureas also promote the catalytic asymmetric intermolecular Michael addition-lactonization of arylacetic acids and α-keto-β,γ-unsaturated esters, giving anti-dihydropyranones with high diastereo- and enantiocontrol (up to 98:2 dr, up to 99% ee).     

Structure-enantioselectivity effects in 3,4-dihydropyrimido[2,1-b]benzothiazole-based isothioureas as enantioselective acylation catalysts

The catalytic activity and enantioselectivity in the kinetic resolution of (±)-1-naphthylethanol with a range of structurally related 3,4-dihydropyrimido[2,1-b]benzothiazole-based catalysts is examined. Of the isothiourea catalysts screened, (2S,3R)-2-phenyl-3-isopropyl substitution proved optimal, giving good levels of selectivity in the kinetic resolution of a number of secondary alcohols (S values up to >100 at ~50% conversion). Low catalyst loadings (0.10-0.25 mol%) of the optimal isothiourea can be used to generate enantiopure alcohols (>99% ee) in good yields.     

Valorisation of bio-oil resulting from fast pyrolysis of wood

Bio-oil resulting from the pyrolysis of lignocellulose is a complex mixture of polar low molecular mass oxygenated compounds of various functionalities and non-polar high molecular mass lignin derivatives. Several approaches to the upgrading of bio-oil are currently in progress. This study investigates the valorisation of crude bio-oil using physical and chemical methods. The effects of methanol addition on some properties of the bio-oil are investigated. Stable bio-oil/diesel oil emulsions are produced by the addition of surfactants with a hydrophilic-lipophilic balance value of 5–6. An alternative approach towards the upgrading of bio-oil is the hydrotreatment of the water-soluble fraction of bio-oil. Two-stage hydroprocessing with noble-metal catalysts Ru/C and Pt/C increases the intrinsic hydrogen content of the water-soluble fraction. The results show that the thermally unstable components including sugars, ketones and aldehydes are readily converted to diols and alcohols at pressures of 5 MPa. These observations can be explained by a set of reaction pathways for the compounds identified.     

Stereodivergent Organocatalytic Intramolecular Michael Addition/Lactonization for the Asymmetric Synthesis of Substituted Dihydrobenzofurans and Tetrahydrofurans

A stereodivergent asymmetric Lewis base catalyzed Michael addition/lactonization of enone acids into substituted dihydrobenzofuran and tetrahydrofuran derivatives is reported. Commercially available (S)‐(?)‐tetramisole hydrochloride gives products with high syn diastereoselectivity in excellent enantioselectivity (up to 99:1 d.r._syn/anti, 99 % ee_syn), whereas using a cinchona alkaloid derived catalyst gives the corresponding anti‐diastereoisomers as the major product (up to 10:90 d.r._syn/anti, 99 % ee_anti).     

Evaluation of pulsed radiofrequency glow discharge time-of-flight mass spectrometry for precious metal determination in lead fire assay buttons

In this paper, an exploration of the capabilities and limitations of pulsed radiofrequency glow discharge time-of-flight mass spectrometry (GD-TOFMS) for the determination of the precious metals Ag, Au, Pd, Pt and Rh in lead buttons obtained by Pb fire assay is reported on. Since the matrix consists almost entirely of lead (>99%), the occurrence of doubly charged Pb (Pb²⁺) ions can hinder accurate determination of Rh. This problem was counteracted by relying on the time-resolved formation of different ion types over the pulse period of the glow discharge, which allows discrimination against the Pb²⁺ ions. The formation of ArCu⁺ ions as a result of the use of a copper anode was assessed to pose no threat to the accuracy of the results obtained for the set of samples analyzed as its contribution to the total signal at m/z = 103 could be adequately corrected for. The method developed was evaluated in terms of accuracy and precision using a set of Pb button standards with analyte concentrations between 5 and 100 μg g⁻¹. For the purpose of validation, a 10 μg g⁻¹ standard was considered as a sample. Overall, an acceptable accuracy was obtained with a bias of <5% between the experimental results and the corresponding reference values, except for Au, for which a larger deviation occurred. Precision values (repeatability) of typically <5% relative standard deviation (RSD) (for N = 3) were obtained and the limits of detection (LODs) vary from ∼0.020 μg g⁻¹ for Ag to ∼0.080 μg g⁻¹ for Pt.     

Methyl α- -fructofuranoside: Synthesis and conversion into carboxylates

Methyl α- -fructofuranoside was synthesized by methylation of -fructose and subsequent isolation of the α-furanoside from the anomeric mixture. This fructofuranoside was used as a starting material for the syntheses of several carboxylates, applying glycolic oxidation, selective oxidation of the primary alcohol function at the C-6 position and carboxymethylation.     

Complexation of Ln(III) and Ca(II) Cations with 3,4-Dicarboxyinulin and Model Compounds: Methyl 3,4-Dicarboxy-alpha-D-fructofuranoside and 3,4-Dicarboxynystose, As Studied by Multinuclear Magnetic Resonance Spectroscopy and Potentiometry

Complexes of Ln(III) and Ca(II) cations with 3,4-dicarboxyinulin (DCI) and model compounds, methyl 3,4-dicarboxy-alpha-D-fructofuranoside (DCF) and 3,4-dicarboxynystose (DCN) were studied using multinuclear magnetic resonance spectroscopy and potentiometric methods. Complexes of the model compounds with Ln(III) ions provided a feasible way in which to study complexation phenomena of the dicarboxyinulin/Ca(II) system using NMR techniques. Information on complex geometry was derived from the effect of Ln(III) ions on chemical shifts and longitudinal relaxation rates. Metal-ligand stoichiometries of 1:2 and 1:1, in which the ligand coordination was tridentate as well as tetradentate, were found. Potentiometric measurements carried out with Ca(II) yielded information on the stoichiometry as well as the cooperativity of metal ion binding by the ligands.