Mukaiyama–Michael Reactions with trans‐2,5‐Diarylpyrrolidine Catalysts: Enantioselectivity Arises from Attractive Noncovalent Interactions,Not from Steric Hindrance

The scope of the enantioselective Mukaiyama–Michael reactions catalyzed by trans‐2,5‐diphenylpyrrolidine has been expanded to include both α‐ and β‐substituted enals. However, the rationalization of the observed enantioselectivity is far from obvious since the catalyst is not very sterically hindered. DFT calculations were carried out to rationalize the observed stereoselectivities. Transition states of the C?C bond formation between iminium intermediates and silyloxyfurans were located and their relative energies were used to estimate the stereoselectivity data. We find excellent agreement between the predicted and observed stereoselectivities. The analysis of intermolecular forces reveals that the enantioselectivity is mostly due to stabilizing noncovalent interactions between the reacting partners, not due to steric hindrance. The role of attractive noncovalent interactions in enantioselective catalysis may be underappreciated.     

Supramolecular stabilization of N(2)H(7)(+)

The cation N(2)H(7)(+) has been stabilized in a largely hydrophobic supramolecular environment and characterized in the solid state. The cation is situated in the bowl-shaped cavity of calix[4]arene. All of the hydrogen atoms are clearly discernible owing to high-quality X-ray data as well as lack of disorder and symmetry-imposed ambiguity. It appears that electrostatic interactions play a critical role in stabilizing the structure.     

Surface order large deviations for high-density percolation

Summary We derive surface order large deviation estimates for the volume of the largest cluster and for the volume of the largest region surrounded by a cluster of a Bernoulli percolation process restricted to a big finite box, with sufficiently large parameter. We also establish a useful version of the isoperimetric inequality, which is the main tool of our proofs.     

Comparative analysis of the full set of methylated β‐cyclodextrins as chiral selectors in capillary electrophoresis

The chiral separation ability of the full library of methylated‐β‐cyclodextrins towards pharmacologically significant racemic drugs including basic compounds was studied by chiral CE. The syntheses of all the methylated, single isomer β‐cyclodextrins were revised and optimized and the aqueous solubility of the derivatives was unambiguously established. The three most relevant commercially available methylated isomeric mixtures were also included in the screening, so a total of ten various methylated CDs were investigated. The effects of the selector concentration on the enantiorecognition properties at acidic pH were investigated. Among the dimethylated β‐cyclodextrins, the heptakis (2,6‐di‐O‐methyl)‐β‐cyclodextrin isomer (2,6‐DIMEB) resulted to be the most versatile chiral selector. Terbutaline was selected as a model compound for the in‐depth investigation of host‐guest enantiodiscrimination ability. The association constants between the two terbutaline enantiomers and 2,6‐DIMEB were determined in order to support that the enantioseparation is driven by differences is host‐guest binding. The migration order of the enantiomers was confirmed by performing spiking experiments with the pure enantiomers. 1D and 2D NMR spectroscopy was applied to the 2,3‐, and 2,6‐DIMEB/terbutaline systems to rationalize at molecular level the different enantioseparation ability of the dimethylated β‐cyclodextrin selectors.     

Stereoselective synthesis of 3,3-diarylacrylonitriles as tubulin polymerization inhibitors

A series of 3,3-diarylacrylonitriles were synthesized stereoselectively as tubulin polymerization inhibitors for potential use in cancer chemotherapy. This synthetic route features stannylcupration and palladium-catalyzed Stille cross-coupling chemistry, allowing both E and Z isomers of 3,3-diarylacrylonitriles to be prepared in a very short sequence of reactions.     

Water-repellent acylated and silylated wood samples and their surface analytical characterization

The interest for chemical modification of wood with the aim of preserving it from physical and biochemical deterioration is rapidly increasing. Among the possibilities, acetylation has a great potential for improving the dimension instability of wood against moisture and the durability of wooden objects. Recently, a new acetylating agent, isopropenyl acetate has attracted attention giving an improved acetylating method. By increasing the size of the acyl group, a positive effect on the wood hydrophobicity can be reached. The anhydrides, however, are less reactive. Another applicable surface modification is the silylation of wood that renders the wood surface hydrophobic.

In this paper, we report about the acylation and silylation of different wood samples. A new manufacturing process is tested in which low-value Eucalyptus wood is mixed acylated. The reagent mixture contains at least two kinds of acyl group. One of them is acetyl group; the other(s) can be user-defined. We also report about a silylation method, in which catalyst facilitates the chemisorption process. The extent of modification of the treated wood samples was evaluated by means of weight percent gain, ATR-FTIR, and pyrolysis-gas chromatography–mass spectrometry (Py-GC/MS). Methylene blue adsorption of selected samples was also studied. The result of analytical measurements was in agreement with that of wettability studies.     

Precise large deviation estimates for a one-dimensional random walk in a random environment

ω_x } (taking values in the interval [1/2, 1)), which serve as an environment. This environment defines a random walk {X _k } (called a RWRE) which, when at x, moves one step to the right with probability ω _x , and one step to the left with probability 1 −ωx. Solomon (1975) determined the almost-sure asymptotic speed (= rate of escape) of a RWRE, in a more general set-up. Dembo, Peres and Zeitouni (1996), following earlier work by Greven and den Hollander (1994) on the quenched case, have computed rough tail asymptotics for the empirical mean of the annealed RWRE. They conjectured the form of the rate function in a full LDP. We prove in this paper their conjecture. The proof is based on a “coarse graining scheme” together with comparison techniques. Received: 22 July 1997/Revised version: 15 June 1998