Electron delocalization in linearly pi-conjugated systems: a concept for quantitative analysis

Donor- and/or acceptor-substituted pi-conjugated systems represent an important class of compounds in organic chemistry. However, up to now, a general method to quantitatively address the efficiency of a conjugated path is still missing. In this work, a novel computational approach based on deletion energies and on second-order orbital interaction energies in a natural bond orbital (NBO) scheme is employed to quantitatively assess ("measure") delocalization energies. Moreover, the purpose of this work is to assess the efficiency of distinct pi-conjugated paths, that is, geminal, cis, and trans, as well as to predict the impact of substituents on a given backbone. This study is focused on various mono-, di-, tri-, and tetrasubstituted tetraethynylethenes (TEEs). These model systems are suitable for our analysis, because they offer distinct conjugation paths within the same molecule, and can also be substituted in multiple ways. Differences between conjugation paths, the effect of neighbor paths, and the impact of donor and acceptor substituents on the various paths are discussed.     

Synthesis and lectin binding ability of glycosamino acid-calixarenes exposing GlcNAc clusters

Novel calix[4 or 8]arene-based glycoconjugates exposing terminal N-acetyl-D-glucosamine clusters have been synthesized using amino acid-calixarenes as building blocks. The obtained glycosamino acid-calixarenes 9b-14b have lectin-binding ability and amplified inhibitory effects on erythrocyte agglutination induced by wheat germ (Triticum vulgaris) agglutinin (WGA). The inhibitory ability is dependent on the presence of the spacer and on the shape and rigidity of the calixarene skeleton.     

Novel rearrangements of 4-silyl-3-buten-2-ones

Two 4-silyl-3-buten-2-ones, 2a and 2c, underwent an interesting rearrangement involving migration of the allyl or phenyl group on the silicon atom to the adjacent enone carbon when treated with various bases.     

New synthesis of pyrrolidine homoazasugars via aminohomologation of furanoses and their use for the stereoselective synthesis of aza-C-disaccharides

The introduction of a formyl group at the anomeric center of 2,3,5-tri-O-benzyl furanoses and substitution of the ring oxygen with a basic nitrogen atom (aminohomologation) was carried out via stereoselective addition of 2-lithiothiazole to N-benzyl, N-furanosylhydroxylamines (masked N-benzyl sugar nitrones), followed by reductive dehydroxylation of the resulting open-chain adducts, and then ring closure via intramolecular displacement of the free hydroxy group by the amino group and unmasking of the formyl group from the thiazole ring. The resulting formyl aza-C-glycosides were transformed into 2,5-dideoxy-2,5-imino-hexitols (pyrrolidine homoazasugars) by reduction of the formyl to the hydroxymethyl group and removal of the O- and N-benzyl groups by hydrogenolysis. This reaction sequence was applied to four furanoses (D-arabino, D-ribo, D-lyxo, L-xylo) to give the hydroxy- and amino-free homoazasugars, including the natural product 2,5-dideoxy-2,5-imino-D-mannitol, in 17% overall yields (six steps). The formyl aza-C-glycosides proved to be valuable intermediates for the synthesis of more complex derivatives. In fact, these sugar aldehydes were employed in Wittig-type coupling reactions with galactose and ribose phosphoranes to give bis-glycosylated alkenes, which upon reduction of the double bond were transformed into methylene isosteres of (1-->6)- and (1-->5)-linked disaccharides in which one of the two sugar moieties was an azasugar (aza-(1-->x)-C-disaccharides).     

Nonmonotone Algorithms for Pattern Search Methods

This work deals with the solution of ill-conditioned unconstrained minimization problems by means of pattern search methods. To this end, the usual requirement of monotonic reduction of the objective function is relaxed and nonmonotone pattern search methods are proposed, which maintain the convergence properties of their monotone counterparts. Numerical experimentation on several well-known ill-conditioned functions is reported. The results highlight a class of pattern search methods which benefit very much by the introduction of nonmonotone strategies.     

Mechanisms of ablation-rate decrease in multiple-pulse laser ablation

We present two sets of experimental results on the ablation-rate decrease with increase of the number of consecutive laser pulses hitting the same spot on the target surface. We have studied laser ablation of a carbon target with nanosecond pulses in two different interaction regimes: one with a XeCl laser (λ=308 nm) and the other with a Nd:YAG laser (λ=1064 nm), in both cases at the intensity ∼5×10⁸ W/cm² Two different mechanisms were found to be responsible for the ablation-rate decrease; they are directly related to the two different laser–matter interaction regimes. The UV-laser interaction is in the regime of transparent vapour (surface absorption). The increase of the neutral vapour density in the crater produced by the preceding laser pulses is the main reason for the decrease of ablation rate. With the IR laser each single laser pulse interacts with a partially ionised plume. With increase of the number of pulses hitting the same spot on the target surface, the laser–matter interaction regime gradually changes from the near-surface absorption to the volume absorption, resulting in the decrease in absorption in the target and thus in the decrease in the ablation rate. The change in the evaporation rate was considered for both vacuum and reactive-gas environments. Received: 21 February 2001 / Accepted: 26 February 2001 / Published online: 23 May 2001     

Kluyveromyces marxianus CBS 6556 growing cells as a new biocatalyst in the asymmetric reduction of substituted acetophenones

The use of microorganism growing cells is a well recognized methodology in biocatalyzed organic reactions. A non-conventional thermotolerant Kluyveromyces marxianus yeast strain was used for the bio-reduction of different arylketones. Differently substituted ketones were converted into the corresponding (S)-alcohols with up to 96% enantiomeric excess under very mild reaction conditions. Kluyveromyces marxianus represents a promising biocatalyst for the production of optically active 1-arylethanols.     

Pd(II) complexes of monodentate deoxycholic acid derived binaphthyl diamido phosphites as chiral catalysts in the asymmetric Suzuki-Miyaura cross-coupling

Chiral binaphthyl diamidophosphites derived from deoxycholic acid were synthesized and used as ligands for the preparation of mononuclear Pd(II) complexes, which were employed as catalysts in the asymmetric Suzuki-Miyaura cross-coupling of arylboronic acids with aryl bromides. Among the different reaction parameters, the substrate concentration emerged as being crucial for the outcome of the reaction: the reaction was faster in a concentrated reaction mixture, and could be performed at 0 °C, where the reaction promoted by the Pd-complexes was more enantioselective affording cross-coupling products with ee up to 70%.