Derivatives of (2R)-N-Glyoxylbornane-10,2-sultam and Their Use as auxiliaries in the diastereoselective spirocyclization of 2-substituted tryptamines

A crude hydrate 6 and a crystalline hemiacetal 7 of glyoxylamide 4 were prepared from crotonamide 5 (Scheme 2). Particularly hemiacetal 7 , but also 6 and the ‘dimer’ 8 (obtained from 7 ) may serve as homochiral auxiliaries. The structure of 8 was determined by X-ray analysis. By arenesulfonyl halides, tryptimines 12–14 of 4 were diastereoselectively transformed into spirotricycles 15–17 and 19 .     

An inner product lemma

Given the operator product BA in which both A and B are symmetric positive‐definite operators, for which symmetric positive‐definite operators C is BA symmetric positive‐definite in the C inner product 〈x, y〉C? This question arises naturally in preconditioned iterative solution methods, and will be answered completely here. Copyright © 2004 John Wiley & Sons, Ltd.     

Biopolymers for biocatalysis: Structure and catalytic mechanism of hydroxynitrile lyases

Hydroxynitrile lyases catalyze the reversible cleavage of α-cyanohydrins to yield hydrocyanic acid and the corresponding aldehyde or ketone. Besides its biological interest, this class of enzymes is also of relevance in industrial biocatalysis for the enantioselective condensation of HCN with a variety of aldehydes and ketones. Several distinctly different types of hydroxynitrile lyases (HNLs) are known, which must have originated through convergent evolution from different ancestral proteins. Three-dimensional structural data are known for three classes of hydroxynitrile lyases. Insights into the reaction mechanisms emerged from a combination of structural, enzyme kinetic, spectroscopic, and molecular modeling data. For all three types of HNLs, mechanisms involving acid–base catalysis were proposed. In members belonging to the α,β-hydrolase type, the amino acid residues of the catalytic triad presumably act as general acid/base, whereas for flavine adenine dinucleotide (FAD)-dependent HNLs a single histidine residue fulfills this function. In the third type of HNL—which is related to carboxypeptidase—acid–base catalysis involves the carboxylate of the C-terminal residue. The catalytic relevance of a positive electrostatic potential in the active site was suggested in some of the mechanistic proposals. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 479–486, 2004     

Fenchel duality, Fitzpatrick functions and the extension of firmly nonexpansive mappings

Recently, S. Reich and S. Simons provided a novel proof of the Kirszbraun-Valentine extension theorem using Fenchel duality and Fitzpatrick functions. In the same spirit, we provide a new proof of an extension result for firmly nonexpansive mappings with an optimally localized range.

     

A Variable Neighborhood Search for the Multi Depot Vehicle Routing Problem with Time Windows

The aim of this paper is to propose an algorithm based on the philosophy of the Variable Neighborhood Search (VNS) to solve Multi Depot Vehicle Routing Problems with Time Windows. The paper has two main contributions. First, from a technical point of view, it presents the first application of a VNS for this problem and several design issues of VNS algorithms are discussed. Second, from a problem oriented point of view the computational results show that the approach is competitive with an existing Tabu Search algorithm with respect to both solution quality and computation times.     

A geometric theory forL 2-stability of the inverse problem in a one-dimensional elliptic equation from anH 1-observation

This study provides a stability theory for the nonlinear least-squares formulation of estimating the diffusion coefficient in a two-point boundary-value problem from an error-corrupted observation of the state variable. It is based on analysing the projection of the observation on the nonconvex attainable set.This research was started while G. Chavent visited the Technical University of Graz. Support through the Steiermaerkische Landesregierung is gratefully acknowledged.