Asymmetric reduction of acetophenone and propiophenone by NaAl(IPTOLate)H2 combined with enantiomeric enrichment of the reaction product as an inclusion complex with IPTOL

An improved procedure was developed for asymmetric reduction of acetophenone and propiophenone by the chiral reagent NaAl(IPTOLate)H₂. This procedure is based on isolation of the chiral alcohol that formed as a crystalline host—guest complex with the IPTOL ligand. The enantiomeric enrichment of the product was as high as 97% ee. The ability of IPTOL and its analogs to form host—guest complexes with a number of ether-type solvents, 1-phenylethanol, and 1-phenylpropan-1-ol as well as thermal stabilities of IPTOL-containing complexes with these alcohols were studied.     

Density and Volume Properties of Ethane-1,2-diol + 1,2-Dimethoxyethane + Water Ternary Mixtures from −10° to 80°

Thermodynamic interactions in the ethane-1,2-diol (1) + 1,2-dimethoxyethane(2) + water (3) ternary system have been investigated in terms of the excessmolar volume, derived from density measurements at 19 different temperaturesfrom –10;dg to 80;dgC. Fourteen three-component mixtures have been considered,covering the entire composition range. The excess molar volumes are discussedin terms of conformational changes induced in each component by the presenceof another one. The results obtained support the hypothesis of the absence of anythree-component complex adducts under all experimental conditions investigated.     

Elaborate treatment of retention in chemoselective chromatography—The retention increment approach and non-linear effects

The retention increment approach is described which quantifies the association equilibria of a selectand and a selector in complexation and inclusion chromatography. A thermodynamic treatment of enantioselectivity based on retention phenomena in chromatography including entropy/enthalpy compensation and the isoenantioselective temperature is advanced. Kinetic parameters of enantiomerization are discussed. Non-linear effects, both existent and elusive, are described and proposed, respectively. The enantioselectivity pertaining to catalysis vs. chromatography is compared and a unified nomenclature is proposed. Through an educational effort, this account is aimed at providing a deeper insight into chemoselective aspects of chromatography thereby stimulating further research of both established and speculative phenomena of the most intriguing manifestation of chemoselectivity, that is, of enantioselectivity.     

The least square nucleolus is a general nucleolus

This short note proves that the least square nucleolus (Ruiz et al. (1996)) and the lexicographical solution (Sakawa and Nishizaki (1994)) select the same imputation in each game with nonempty imputation set. As a consequence the least square nucleolus is a general nucleolus (Maschler et al. (1992)). Received: December 1998/Revised version: July 1999     

Weak Convergence of the Empirical Mean Excess Process with Application to Estimate the Negative Tail Index

Let Y _i , 1 ≤ i ≤ n be i.i.d. random variables with the generalized Pareto distribution W _γ,σ with γ < 0. We define the empirical mean excess process with respect to {Y _i , 1 ≤ i ≤ n} as in Eq. 2.1 (see below) and investigate its weak convergence. As an application, two new estimators of the negative tail index γ are constructed based on the linear regression to the empirical mean excess function and their consistency and asymptotic normality are obtained.      

Thermodynamics of alcohols and monosaccharides in aqueous solutions of thiourea at 25°C

The excess enthalpies of twelve ternary aqueous solutions of alcohols or monosaccharides containing thiourea have been determined by flow microcalorimetry at 25°C. The coefficients of the virial expansion of the excess enthalpies are compared with those reported in the literature for the same ternary solutions containing urea in place of thiourea. The cross-interaction coefficients are positive for the thiourea-alcohol systems and depend on the length and branching of the alkyl chain of the alcohols. On the other hand, they are negative for the thiourea-monosaccharide systems. Thus, thiourea, as urea, can be used as a probe to reveal differences in the behavior of families of solutes characterized by the same functional groups. The results can be interpreted in terms of the relative stabilities of hydration cospheres of hydrophobic or hydrophilic solutes toward a chaotropic agent such as thiourea.Presented at the sixth Italian meeting on Calorimetry and Thermal Analysis (AICAT) held in Naples, December 4–7, 1984.     

Density, Viscosity, Refractive Index, and Speed of Sound in Binary Mixtures of Pyridine and 1-Alkanols (C6, C7, C8, C10) at 303.15 K

The densities (ρ), viscosities (η), refractive indices (nD), and speeds of sound (u), of binary mixtures of pyridine with 1-hexanol, 1-heptanol, 1-octanol and 1-decanol, including those of pure liquids, were measured over the entire composition range at 303.15 K and atmospheric pressure. From these experimental data, the values of excess molar volumes (VE), deviations in isentropic compressibilities (Δks), viscosities (Δh), molar refractions (ΔRm), apparent and partial molar volumes (Vf,2 and ), apparent and partial molar compressibilities (Kf,2 and ), of alkanols in pyridine and their corresponding deviations (ΔV and ΔK) were calculated. The variations of these parameters with composition of the mixtures suggest that the strength of interactions in these mixtures follow the order: 1-hexanol＞1-heptanol＞1-octanol＞1-decanol. All the excess and deviation functions were fitted to Redlich-Kister polynomial equation to determine the fitting coefficients and the standard deviations.     

Amplification of chirality as a pathway to biological homochirality

Amplification of enantiomeric enrichment is a key feature for the chemical evolution of biological homochirality from the origin of chirality. The aggregations of the enantiomers by diastereomeric interactions enable the modification of their enantiomeric excess during some chemical processes. Fluorine-containing chiral compounds possess large amplification effect via distillation, sublimation and achiral chromatography by self-disproportionation. Asymmetric amplifications in enantioselective catalysis occur by the differential formation and reactivity between homochiral and heterochiral aggregate in solution.We described the amplification of ee in asymmetric autocatalysis of 5-pyrimidyl alkanol in the reaction between diisopropylzinc and pyrimidine-5-carbaldehdye. During the reactions extremely low ee (ca. 0.00005% ee) can be amplified to achieve more than 99.5% ee. Since the proposed origins of chirality such as CPL, quartz, chiral organic crystals of achiral compounds and statistical fluctuation of ee can initiate the asymmetric autocatalysis with amplification of ee, the proposed origin of chirality can be linked with enantiopure organic compound in conjunction with amplification of ee by asymmetric autocatalysis. In addition, we described that the carbon isotopically chiral compound triggers the asymmetric autocatalysis of 5-pyrimiodyl alkanol to afford the enantioenriched product with the absolute configuration correlated with that of carbon isotope chirality, that is, isotope chirality including hydrogen isotopes can control the enantioselectivity of asymmetric addition of alkyl metal reagent to aldehyde.     

Phosphine and Thiophene Cyclopalladated Complexes: Hydrolysis Reactions in Strong Acidic Media

The mechanisms for the hydrolysis of organopalladium complexes [Pd(CNN)R]BF₄ (R=P(OPh)₃, PPh₃, and SC₄H₈) were investigated at 25 °C by using UV/Vis absorbance measurements in 10 % v/v ethanol/water mixtures containing different sulphuric acid concentrations in the 1.3–11.7 M range. In all cases, a biphasic behavior was observed with rate constants k_1obs, which corresponds to the initial step of the hydrolysis reaction, and k_2obs, where k_1obs>k_2obs. The plots of k_1obs and k_2obs versus sulfuric acid concentration suggest a change in the reaction mechanism. The change with respect to the k_1obs value corresponds to 35 %, 2 %, and 99 % of the protonated complexes for R=PPh₃, P(OPh)₃, and SC₄H₈, respectively. Regarding k_2obs, the change occurred in all cases at about 6.5 M H₂SO₄ and matched up with the results reported for the hydrolysis of the 2‐acetylpyridinephenylhydrazone (CNN) ligand. By using the excess acidity method, the mechanisms were elucidated by carefully looking at the variation of k_i,_obs (i=1,2) versus ${c_{{\rm{H}}^ + } }$ . The rate‐determining constants, k_0,A‐1, k_0,A‐2, and k_0,A‐SE2 were evaluated in all cases. The R=P(OPh)₃ complex was most reactive due to its π‐acid character, which favors the rupture of the trans nitrogen–palladium bond in the A‐2 mechanism and also that of the pyridine nitrogen–palladium bond in the A‐1 mechanism. The organometallic bond exerts no effect on the relative basicity of the complexes, which are strongly reliant on the substituent.