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  • 2000-2004  (481)
  • 1890-1899
  • 2001  (43)
  • 2000  (438)
  • General Chemistry  (378)
  • ddc:000  (103)
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Years
  • 2000-2004  (481)
  • 1890-1899
Year
Language
  • 1
    Publication Date: 2014-11-10
    Description: An edge of a perfect graph $G$ is critical if $G-e$ is imperfect. We would like to decide whether $G - e$ is still {\sl almost perfect} or already {\sl very imperfect}. Via relaxations of the stable set polytope of a graph, we define two superclasses of perfect graphs: rank-perfect and weakly rank-perfect graphs. Membership in those two classes indicates how far an imperfect graph is away from being perfect. We study the cases, when a critical edge is removed from the line graph of a bipartite graph or from the complement of such a graph.
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    Language: English
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  • 2
    Publication Date: 2020-03-06
    Description: Collection of abstracts of the first SIAM-EMS conference Applied Mathematics in our Changing World'' in Berlin, September 2-6, 2001.
    Keywords: ddc:000
    Language: English
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  • 3
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    Publication Date: 2020-02-11
    Description: {\sc Zimpl} is a little language to translate the mathematical model of a problem into a linear or (mixed-)integer mathematical program expressed in {\tt lp} or {\tt mps} file format which can be read by a LP or MIP solver.
    Keywords: ddc:000
    Language: English
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  • 4
    Publication Date: 2014-02-26
    Description: Im ersten Teil des folgenden Aufsatzes werden allgemeine Überlegungen zur Entwicklung von Bibliotheken hin zu Informationsvermittlungsstellen für sowohl elektronische wie auch gedruckte Medien angestellt. Basierend auf den Ergebnissen der Evaluation digitaler Bibliotheken und Informationsportale in Deutschland wird ein erster Kriterienkatalog für ein Verbund-Informationsportal für den Kooperativen Bibliotheksverbund Berlin-Brandenburg entwickelt. Im Anhang befindet sich der Statusbericht über Informationsportale und digitale Bibliotheken in Deutschland. Dazu wurden sieben digitale Bibliotheken auf Verbundebene und 21 Bibliotheken nach Bundesländern evaluiert.
    Keywords: ddc:000
    Language: German
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  • 5
    Publication Date: 2020-11-13
    Description: Given a set of service requests (events), a set of guided servers (units), and a set of unguided service contractors (conts), the vehicle dispatching problem {\sl vdp} is the task to find an assignment of events to units and conts as well as tours for all units starting at their current positions and ending at their home positions (dispatch) such that the total cost of the dispatch is minimized. The cost of a dispatch is the sum of unit costs, cont costs, and event costs. Unit costs consist of driving costs, service costs and overtime costs; cont costs consist of a fixed cost per service; event costs consist of late costs linear in the late time, which occur whenever the service of the event starts later than its deadline. The program \textsf{ZIBDIP} based on dynamic column generation and set partitioning yields solutions on heavy-load real-world instances (215 events, 95 units) in less than a minute that are no worse than 1\% from optimum on state-of-the-art personal computers.
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    Language: English
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  • 6
    Publication Date: 2021-02-01
    Description: Scenario tree models of stochastic programs arise naturally under standard nonanticipativity assumptions. We demonstrate how tree-sparse programs cover the general case, with \emph{arbitrary} information constraints. Detailed examples and intuitive interpretations illuminate the basic thoughts behind the abstract but elementary construction.
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    Language: English
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  • 7
    Publication Date: 2020-03-09
    Description: In this paper we present an algorithm that accelerates 3D texture-based volume rendering of large and sparse data sets. A hierarchical data structure (known as AMR tree) consisting of nested uniform grids is employed in order to efficiently encode regions of interest. The hierarchies resulting from this kind of space partitioning yield a good balance between the amount of volume to render and the number of texture bricks -- a prerequisite for fast rendering. Comparing our approach to an octree based algorithm we show that our algorithm increases rendering performance significantly for sparse data. A further advantage is that less parameter tuning is necessary.
    Keywords: ddc:000
    Language: English
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  • 8
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    Publication Date: 2019-10-24
    Keywords: ddc:000
    Language: German
    Type: annualzib , doc-type:report
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  • 9
    Publication Date: 2021-02-01
    Description: Mathematical optimization techniques are on their way to becoming a standard tool in chemical process engineering. While such approaches are usually based on deterministic models, uncertainties such as external disturbances play a significant role in many real-life applications. The present article gives an introduction to practical issues of process operation and to basic mathematical concepts required for the explicit treatment of uncertainties by stochastic optimization.
    Keywords: ddc:000
    Language: English
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  • 10
    Publication Date: 2014-02-26
    Description: Uncoupling-coupling Monte Carlo (UCMC) combines uncoupling techniques for finite Markov chains with Markov chain Monte Carlo methodology. UCMC aims at avoiding the typical metastable or trapping behavior of Monte Carlo techniques. From the viewpoint of Monte Carlo, a slowly converging long-time Markov chain is replaced by a limited number of rapidly mixing short-time ones. Therefore, the state space of the chain has to be hierarchically decomposed into its metastable conformations. This is done by means of combining the technique of conformation analysis as recently introduced by the authors, and appropriate annealing strategies. We present a detailed examination of the uncoupling-coupling procedure which uncovers its theoretical background, and illustrates the hierarchical algorithmic approach. Furthermore, application of the UCMC algorithm to the $n$-pentane molecule allows us to discuss the effect of its crucial steps in a typical molecular scenario.
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  • 11
    Publication Date: 2021-02-01
    Description: Standard model predictive control for real-time operation of industrial production processes may be inefficient in the presence of substantial uncertainties. To avoid overly conservative disturbance corrections while ensuring safe operation, random influences should be taken into account explicitly. We propose a multistage stochastic programming approach within the model predictive control framework and apply it to a distillation process with a feed tank buffering external sources. A preliminary comparison to a probabilistic constraints approach is given and first computational results for the distillation process are presented.
    Keywords: ddc:000
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  • 12
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    Publication Date: 2021-02-01
    Description: Dynamic stochastic programs are prototypical for optimization problems with an inherent tree structure inducing characteristic sparsity patterns in the KKT systems of interior methods. We propose an integrated modeling and solution approach for such tree-sparse programs. Three closely related natural formulations are theoretically analyzed from a control-theoretic viewpoint and compared to each other. Associated KKT solution algorithms with linear complexity are developed and comparisons to other interior approaches and related problem formulations are discussed.
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    Language: English
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  • 13
    Publication Date: 2020-11-13
    Description: We introduce a new problem that was motivated by a (more complicated) problem arising in a robotized assembly enviroment. The bin coloring problem is to pack unit size colored items into bins, such that the maximum number of different colors per bin is minimized. Each bin has size~$B\in\mathbb{N}$. The packing process is subject to the constraint that at any moment in time at most $q\in\mathbb{N}$ bins may be partially filled. Moreover, bins may only be closed if they are filled completely. An online algorithm must pack each item must be packed without knowledge of any future items. We investigate the existence of competitive online algorithms for the online uniform binpacking problem. We show upper bounds for the bin coloring problem. We prove an upper bound of $3q$ - 1 and a lower bound of $2q$ for the competitive ratio of a natural greedy-type algorithm, and show that surprisingly a trivial algorithm which uses only one open bin has a strictly better competitive ratio of $2q$ - 1. Morever, we show that any deterministic algorithm has a competitive ratio $\Omega (q)$ and that randomization does not improve this lower bound even when the adversary is oblivious.
    Keywords: ddc:000
    Language: English
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  • 14
    Publication Date: 2014-02-26
    Description: In circuit switching networks call streams are characterized by their mean and peakedness (two-moment method). The $GI/M/C/0$ system is used to model a single link, where the $GI$-stream is determined by fitting moments appropriately. For the moments of the overflow traffic of a $GI/M/C/0$ system there are efficient numerical algorithms available. However, for the moments of the freed carried traffic, defined as the moments of a virtual link of infinite capacity to which the process of calls accepted by the link (carried arrival process) is virtually directed and where the virtual calls get fresh exponential i.i.d.\ holding times, only complex numerical algorithms are available. This is the reason why the concept of the freed carried traffic is not used rigorously. The main result of this paper is an efficient algorithm for computing the moments of the freed carried traffic, in particular an explicit formula for its peakedness. This result offers a unified handling of both overflow and carried traffics in networks. Furthermore, some refined characteristics for the overflow and freed carried streams are derived.
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  • 15
    Publication Date: 2014-02-26
    Description: In this work we concentrate on developing methods which determine good lower bounds for set partitioning problems (SPP) in an appropriate amount of time. We found out that it makes sense to use the Lagrangian relaxation method for this task. The Lagrangian relaxed problem of SPP has a simple structure, which leads to algorithms and heuristics, whose total complexity per iteration depends linearly on the number of non-zeros of the problem matrix of SPP. In contrast, other methods like simplex methods or interior point methods have a complexity of higher order. Because the problem matrices of our tested instances are sparse, the linear dependence becomes an advantage for the algorithms and heuristics mentioned above. As a reference for the state-of-the-art we have applied the dual simplex method and the barrier function method, implemented in CPLEX. The methods, which we have developed and compared with those of CPLEX, are SBM, CAM, CCBM, and CBM. SBM is a subgradient bundle method derived from the basic subgradient method, which is a global convergent method for determining the maximum of concave functions. CAM is a coordinate ascent method, where the convex coordinate bundle method CCBM and the coordinate bundle method CBM are derivatives from CAM. We observed that the basic subgradient and the coordinate ascent method are improved if bundling techniques can be used. But the motivation for bundling differs for both approaches. In the former case bundling helps to approximate a minimum norm subgradient, which provides a steepest ascent direction, in order to speed up the performance. In the latter case bundling enables proceeding along directions, which are not restricted on the coordinate directions. By this the performance is accelerated. Among all used techniques stabilization is worth mentioning. Stabilization improves the performance especially at the beginning by avoiding too big steps during the proceeding. This leads to a more stabilized progression. Stabilization was successfully applied to SBM, CAM, CCBM, and CBM. As an overall result we conclude the following: \begin{enumerate} \item CPLEX computes the optimal objective values, whereas SBM and CBM has on average a gap of under $1.5\%$. \item In comparison to CPLEX baropt, SBM, CAM, and CBM the algorithm CCBM has a slow convergence because of the convex combination of ascent coordinate directions. An alternative is to relax the convex combination to a simple sum of the corresponding directions. This idea is realized in CBM. \item If we focus on the running time rather than on optimality then CBM is on average the fastest algorithm. \end{enumerate} Note that methods like SBM or CBM are applied on static SPP instances in order to determine a good lower bound. For solving SPP we need dynamical methods. Due to the complex topic of dynamical methods we will not discuss them, but a certain technique is worth mentioning. It is called column generation. We have indicated that this technique needs good Lagrangian multipliers of the corresponding SPP instances in order to generate further columns (in our case duties), which are added to the current SPP instance. Those multipliers are by-products of methods like our six considered methods. Due to the large number of such generation steps the running time depends on the computation time of these methods. Therefore, CBM fits more to this technique than CPLEX baropt or SBM. To sum it up it can be said that applications such as a duty scheduling can be described as set partitioning problems, whose lower bound can be solved by simplex, interior points, subgradient, or coordinate ascent methods. It turns out that the interior points method CPLEX baropt and the heuristic CBM have good performances. Furthermore, good Lagrangian multipliers, which are by-products of these methods, can be used by techniques like column generation. For this particular technique it also turns out that among our tested algorithms CBM is the most efficient one. In general we can state that real-world applications, which have to solve a large number of Lagrangian relaxed SPP instances can improve their performance by using CBM.
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  • 16
    Publication Date: 2014-02-26
    Description: The success of large-scale multi-national projects like the forthcoming analysis of the LHC particle collision data at CERN relies to a great extent on the ability to efficiently utilize computing a management software (Datagrid, Globus, etc.), while the effective integration of computing nodes has been largely neglected up to now. This is the focus of our work. We present a framework for a high-performance cluster that can be used as a reliable computing node in the Grid. We outline the cluster architecture, the management of distributed data and the seamless intergration of the cluster into the Grid environment.
    Keywords: ddc:000
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  • 17
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    Publication Date: 2020-11-13
    Description: Der Aufsatz ist die ausgearbeitete Fassung eines Vortrages, gehalten am 05.04.2001 auf dem 91. Deutschen Bibliothekartag in Bielefeld. Der Kooperative Bibliotheksverbund Berlin-Brandenburg (KOBV) ist im Rahmen eines wissenschaftlichen Projektes in den Jahren 1997 bis 2000 am Konrad-Zuse-Zentrum für Informationstechnik Berlin (ZIB) aufgebaut worden. Nachdem das Projekt erfolgreich abgeschlossen ist, wird der KOBV 2001 institutionalisiert. In dem Vortrag hat die Verfasserin einen Überblick über das bisher Erreichte, den derzeitigen Stand und die Perspektiven des neuen Verbundes gegeben. Der KOBV stellt eine neue Art von Bibliotheksverbund dar. Sein technisches Konzept und sein organisatorischer Aufbau basieren auf der {\sl Internetphilosophie}. Den informationstechnischen Kern bildet eine Suchmaschine, die die heterogenen lokalen Bibliothekssysteme miteinander verbindet. Die KOBV-Organisation ist dezentral. Sie wird getragen von der Kooperation der Bibliotheken in Berlin und Brandenburg. Eine kleine Verbundzentrale koordiniert dieses Geflecht vernetzter lokaler Einheiten, vertritt den KOBV nach außen und arbeitet - in Form von Projekten - an seiner Weiterentwicklung. Der Entwicklungsaspekt und die Nutzerorientierung sind zwei wesentliche Komponenten in der Verbundarbeit. Berlin und Brandenburg haben auf engem Raum zahlreiche Bibliotheken mit großen, reichhaltigen Medienbeständen. Mittel- bis langfristig sollen Bibliotheken aller Sparten und Größen in den KOBV integriert werden, seien es wissenschaftliche Universalbibliotheken, universitäre Bibliothekssysteme, Spezialbibliotheken, Behörden- und Parlamentsbibliotheken oder öffentliche Bibliotheken. Auch regionale Bibliotheksverbünde können als Subverbünde am KOBV teilnehmen. Mit der KOBV-Suchmaschine ist eine offene Plattform geschaffen worden, auf der weitere Entwicklungen aufsetzen können. Der Aufbau einer virtuellen Regionalbibliothek mit Bestell- und Lieferkomponenten ist eines der Ziele. Darüber hinaus ist es die Vision, in der Region ein virtuelles {\sl Wissensportal} aufzubauen, das dem Nutzer unter einer Adresse den umfassenden Zugang und die umfassende Bereitstellung von Informationen aller Art bietet.
    Keywords: ddc:000
    Language: German
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  • 18
    Publication Date: 2019-01-29
    Description: A new approach to the numerical solution of optimal control problems including control and state constraints is presented. Like hybrid methods, the approach aims at combining the advantages of direct and indirect methods. Unlike hybrid methods, however, our method is directly based on interior-point concepts in function space --- realized via an adaptive multilevel scheme applied to the complementarity formulation and numerical continuation along the central path. Existence of the central path and its continuation towards the solution point is analyzed in some theoretical detail. An adaptive stepsize control with respect to the duality gap parameter is worked out in the framework of affine invariant inexact Newton methods. Finally, the performance of a first version of our new type of algorithm is documented by the successful treatment of the well-known intricate windshear problem.
    Keywords: ddc:000
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  • 19
    Publication Date: 2014-02-26
    Description: Das \emph{Committee on Electronic Information and Communication} (CEIC) der \emph{International Mathematical Union} (IMU) hat die Aufgabe, sich über die langfristige Informationsversorgung in der Mathematik Gedanken zu machen und Lösungsvorschläge hierfür zu erarbeiten. Das Kernthema ist natürlich "`Elektronisches Publizieren"'. Dazu gehören auch Copyright-Regelungen. % Sie sind -- % neben einer Andeutung der weiteren CEIC-Pläne -- der Fokus dieses % kurzen Artikels. Er schließt mit einem von der IMU verabschiedeten % Aufruf zu vernünftigem Verhalten bei Copyright-Vereinbarungen. Eine % nachhaltige Befolgung dieses Aufrufs -- verbunden mit weiteren % Aktivitäten -- könnte die (derzeit kaum noch bezahlbare und % dadurch gefährdete) Literaturversorgung nachhaltig zum Positiven % verändern. Mit diesem Artikel beginnt eine kleine Serie von Aufsätzen, in denen ich (in meiner Funktion als eines von elf CEIC-Mitgliedern) die Empfehlungen des CEIC erläutern werde. % Das heutige Thema sind die % CEIC-Vorschläge zum Copyright
    Keywords: ddc:000
    Language: German
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  • 20
    Publication Date: 2019-05-10
    Description: By computed tomography data (CT), the individual geometry of the mandible is quite well reproduced, also the separation between cortical and trabecular bone. Using anatomical knowledge about the architecture and the functional potential of the masticatory muscles, realistic situations were approximated. The solution of the underlying partial differential equations describing linear elastic material behaviour is provided by an adaptive finite element method. Estimations of the discretization error, local grid refinement, and multilevel techniques guarantee the reliability and efficiency of the method.
    Keywords: ddc:000
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  • 21
    Publication Date: 2021-03-19
    Description: Optimization is the task of finding an optimum solution to a given problem. When the decision variables are discrete we speak of a combinatorial optimization problem. Such a problem is online when decisions have to be made before all data of the problem are known. And we speak of a real-time online problem when online decisions have to be computed within very tight time bounds. This paper surveys the are of combinatorial online and real-time optimization, it discusses, in particular, the concepts with which online and real-time algorithms can be analyzed.
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  • 22
    Publication Date: 2014-02-26
    Description: This paper describes a new simulation tool for the prediction of aerosol formation and behavior in gas--liquid contact devices such as absorbers, scrubbers, quench coolers, and condensers as well as multistage gas cleaning processes, respectively. Aerosol formation can impact severely the separation efficiency of gas cleaning processes. Aerosol or fog formation can arise by spontaneous condensation or desublimation in supersaturated gas phases. The rigorous description of the mass and energy transfer between the gas phase, the liquid phase, and the growing aerosol droplets leads to a system of partial differential and algebraic equations. For the solution of these systems we have developed the plant simulation tool AerCoDe. This program bases upon the linearly--implicit Euler discretisation, which in combination with extrapolation permits an adaptive step size and order control. Typical simulation results of a multistage industrial flue gas scrubbing process are presented. It is shown, that experimental data can be confirmed if the number concentration of condensation nuclei as an input parameter is roughly known.
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  • 23
    Publication Date: 2020-11-13
    Description: This paper discusses online optimization of real-world transportation systems. We concentrate on transportation problems arising in production and manufacturing processes, in particular in company internal logistics. We describe basic techniques to design online optimization algorithms for such systems, but our main focus is decision support for the planner: which online algorithm is the most appropriate one in a particular setting? We show by means of several examples that traditional methods for the evaluation of online algorithms often do not suffice to judge the strengths and weaknesses of online algorithms. We present modifications of well-known evaluation techniques and some new methods, and we argue that the selection of an online algorithm to be employed in practice should be based on a sound combination of several theoretical and practical evaluation criteria, including simulation.
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  • 24
    Publication Date: 2014-02-26
    Description: Wireless communication networks employ radio frequencies to establish communication links. The available radio spectrum is very limited. To meet today's radio communication demand, this resource has to be administered and reused carefully in order to control mutual interference. The reuse can be organized via separation in space, time, or frequency, for example. The problem, therefore, arises to distribute frequencies to links in a ``reasonable manner''. This is the basic form of the frequency assignment problem. What ``reasonable'' means, how to quantify this measure of quality, which technical side constraints to consider cannot be answered in general. The exact specification of this task and its mathematical model depend heavily on the particular application considered. In this paper we discuss this issue with respect to the GSM standard for mobile communication.
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  • 25
    Publication Date: 2014-02-26
    Description: This paper is a summary of the Round Table: ``The Impact of Mathematical Research on Industry and Vice Versa'' held at 3ecm in Barcelona on July 11, 2000. The round table started with contributions of the three panelists. Irene Fonseca, the panel chair, opened the discussion by stating six questions addressing the main issues of the round table topic. She presented the panel's answers to these questions, drawing on many examples from her own academic experience. In the following additional presentations, the other two panel members added further points of view based on their personal involvement with industry. The round table ended with a lively discussion with members from the audience. This written summary of the oral presentations follows the structure of the round table indicated above.
    Keywords: ddc:000
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  • 26
    Publication Date: 2020-03-09
    Description: This article is about \emph{adaptive column generation techniques} for the solution of duty scheduling problems in public transit. The current optimization status is exploited in an adaptive approach to guide the subroutines for duty generation, LP resolution, and schedule construction toward relevant parts of a large problem. Computational results for three European scenarios are reported.
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  • 27
    Publication Date: 2014-02-26
    Description: The recent spectral bundle method allows to compute, within reasonable time, approximate dual solutions of large scale semidefinite quadratic 0-1 programming relaxations. We show that it also generates a sequence of primal approximations that converge to a primal optimal solution. Separating with respect to these approximations gives rise to a cutting plane algorithm that converges to the optimal solution under reasonable assumptions on the separation oracle and the feasible set. We have implemented a practical variant of the cutting plane algorithm for improving semidefinite relaxations of constrained quadratic 0-1 programming problems by odd-cycle inequalities. We also consider separating odd-cycle inequalities with respect to a larger support than given by the cost matrix and present a heuristic for selecting this support. Our preliminary computational results for max-cut instances on toroidal grid graphs and balanced bisection instances indicate that warm start is highly efficient and that enlarging the support may sometimes improve the quality of relaxations considerably.
    Keywords: ddc:000
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  • 28
    Publication Date: 2014-02-26
    Description: Der Wissenschaftsrat hat in seiner Juli-Sitzung 2001 \glqq Empfehlungen zur digitalen Informationsversorgung durch Hochschulbibliotheken \grqq verabschiedet. Einige der Vorschläge des Wissenschaftsrates können, falls sie von den angesprochenen Institutionen aufgenommen werden, zu einer nachhaltigen Veränderung der wissenschaftlichen Informationslandschaft führen. In meinem kurzen Kommentar zu diesem Papier möchte ich auf einige dieser Anregungen hinweisen.
    Keywords: ddc:000
    Language: German
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  • 29
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    Publication Date: 2014-02-26
    Description: Von welcher "Informationsumwelt" träumt jemand, der für seine wissenschaftliche (und sonstige) Arbeit digitale Informationstechnologie intensiv einsetzt? In diesem Artikel beschreibe ich meinen "digitalen Traum". Er ist ganz einfach zu formulieren:"Ich will alles und zwar sofort, jederzeit, "überall" und kostenlos zur Verfügung haben." Ich schildere, was davon heute schon (fast) realisiert ist und was noch fehlt. Ich skizziere einige zentrale Schwierigkeiten der vollständigen Realisierung und skizziere mögliche Lösungen.
    Keywords: ddc:000
    Language: German
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  • 30
    Publication Date: 2019-01-24
    Description: Im Rahmen der biomechanischen Simulation knöcherner Organe ist die Frage nach einer befriedigenden Materialbeschreibung nach wie vor ungelöst. Computertomographische Datensätze liefern eine räumliche Verteilung der (Röntgen-)Dichte und ermöglichen damit eine gute Darstellung der individuellen Geometrie. Weiter können die verschiedenen Materialbestandteile des Knochens, Spongiosa und Kortikalis, voneinander getrennt werden. Aber die richtungsabängige Information der Materialanisotropie ist verloren. In dieser Arbeit wird ein Ansatz für eine anisotrope Materialbeschreibung vorgestellt, die es ermöglicht, den Einfluss der individuellen knöchernen Struktur auf das makroskopische Materialverhalten abzuschätzen.
    Keywords: ddc:000
    Language: German
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  • 31
    Publication Date: 2020-03-09
    Description: Many phenomena in nature and engineering happen simultaneously on rather diverse spatial and temporal scales, i.e.\ exhibit a multi-scale character. Therefore various hierarchical data structures and numerical schemes have been devised to represent quantitatively such phenomena. A special numerical multilevel technique, associated with a particular hierarchical data structure, is so-called Adaptive Mesh Refinement (AMR). This scheme achieves locally very high spatial and temporal resolutions. Due to its popularity, many scientists are in need of interactive visualization tools for AMR data. In this article we present a 3D texture-based volume rendering algorithm for AMR data, that directly utilizes the hierarchical structure. Thereby interactive rendering even for large data sets is achieved. In particular the problems of interpolation artifacts, opacity corrections, and texture memory limitations are addressed. The algorithm's value in practice is demonstrated with simulation and image data.
    Keywords: ddc:000
    Language: English
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  • 32
    Publication Date: 2020-03-09
    Description: By combining techniques of preparation, histology, confocal microscopy, data visualization and data processing, we have created and recently published a standard brain model for drosophila and honey bee brains. This report describes the algorithms and implementation of the corresponding software modules. At the same time it serves as a user's guide for scientist who want to reproduce the results for differerent species or mutants.
    Keywords: ddc:000
    Language: English
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  • 33
    Publication Date: 2014-02-26
    Description: Several classes of systems of evolution equations with one or two vector unknowns are considered. We investigate also systems with one vector and one scalar unknown. For these classes all equations having the simplest higher symmetry are listed.
    Keywords: ddc:000
    Language: English
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  • 34
    Publication Date: 2014-02-26
    Description: Two traffic streams $\Phi_1$, $\Phi_2$ are offered a link. The calls of $\Phi_i$ require exponential holding times with parameter $\mu$ and are accepted if less than $C_i$ trunks are occupied. Approximating the $\Phi_i$ by appropriate renewal processes meeting their first two moments, defined as the moments of the numbers of calls in virtual links of infinite capacity to which the traffic streams as freed traffics are virtually directed and where the calls get fresh exponential i.i.d.\ holding times with parameter $\mu$, stable recursive algorithms of complexity $O(\max(C_1,C_2))$ are derived for the first two defined as above moments of the individual overflow and freed carried traffics. The results offer a unified handling of both overflow and carried traffics in circuit switching networks with trunk reservation, providing a basis for new two-moment network dimensioning algorithms.
    Keywords: ddc:000
    Language: English
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  • 35
    Publication Date: 2014-02-26
    Description: We study the performance of QCD simulations with dynamical Wilson fermions by combining the Hybrid Monte Carlo algorithm with parallel tempering on $10^4$ and $12^4$ lattices. In order to compare tempered with standard simulations, covariance matrices between sub-ensembles have to be formulated and evaluated using the general properties of autocorrelations of the parallel tempering algorithm. We find that rendering the hopping parameter $\kappa$ dynamical does not lead to an essential improvement. We point out possible reasons for this observation and discuss more suitable ways of applying parallel tempering to QCD.
    Keywords: ddc:000
    Language: English
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  • 36
    Publication Date: 2020-11-13
    Description: Dem vorliegenden Aufsatz liegt ein Vortrag zugrunde, den die Verfasserin auf der Ersten Gemeinsamen Fachtagung der DBV-Landesverbände Berlin und Brandenburg "Wir machen den Weg frei : Fusionen - Kooperationen in Berlin und Brandenburg" am 17. Oktober 2001 gehalten hat, in der Vortragsreihe "Möglichkeiten und Grenzen von Ausleih- und bibliographischen Verbünden - VÖB Berlin, VÖB Brandenburg, KOBV". Der Kooperative Bibliotheksverbund Berlin-Brandenburg (KOBV) ist angetreten, um auf der Basis neuer Technologien zeitgemäße, nutzerorientierte Dienstleistungen für den Informationsbereich zu entwickeln und die Informationsinfrastruktur in der Region Berlin-Brandenburg neu zu organisieren. Dabei setzt der KOBV insbesondere auf das Internet. Die Verfasserin beschreibt die einzelnen Stufen, in denen die Dienste des KOBV aufgebaut wurden und kontinuierlich weiter ausgebaut werden. Dabei zeigt sie Vorteile auf, die Nutzern und Bibliotheken durch den Verbund entstehen, und lotet gleichzeitig die Grenzen aus, die dem Verbund gesetzt sind.
    Keywords: ddc:000
    Language: German
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  • 37
    Publication Date: 2014-02-26
    Description: We report numerical results for SBmethod --- a publically available implementation of the spectral bundle method --- applied to the 7$^{th}$ DIMACS challenge test sets that are semidefinite relaxations of combinatorial optimization problems. The performance of the code is heavily influenced by parameters that control bundle update and eigenvalue computation. Unfortunately, no mathematically sound guidelines for setting them are known. Based on our experience with SBmethod, we propose heuristics for dynamically updating the parameters as well as a heuristc for improving the starting point. These are now the default settings of SBmethod Version 1.1. We compare their performance on the DIMACS instances to our previous best choices for Version 1.0. SBmethod Version 1.1 is also part of the independent DIMACS benchmark by H.~Mittelmann. Based on these results we try to analyze strengths and weaknesses of our approach in comparison to other codes for large scale semidefinite programming.
    Keywords: ddc:000
    Language: English
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  • 38
    Publication Date: 2014-11-10
    Description: Many {\cal NP}-hard graph problems can be solved in polynomial time for graphs with bounded treewidth. Equivalent results are known for pathwidth and branchwidth. In recent years, several studies have shown that this result is not only of theoretical interest but can successfully be applied to find (almost) optimal solutions or lower bounds for diverse optimization problems. To apply a tree decomposition approach, the treewidth of the graph has to be determined, independently of the application at hand. Although for fixed $k$, linear time algorithms exist to solve the decision problem ``treewidth $\leq k$'', their practical use is very limited. The computational tractability of treewidth has been rarely studied so far. In this paper, we compare four heuristics and two lower bounds for instances from applications such as the frequency assignment problem and the vertex coloring problem. Three of the heuristics are based on well-known algorithms to recognize triangulated graphs. The fourth heuristic recursively improves a tree decomposition by the computation of minimal separating vertex sets in subgraphs. Lower bounds can be computed from maximal cliques and the minimum degree of induced subgraphs. A computational analysis shows that the treewidth of several graphs can be identified by these methods. For other graphs, however, more sophisticated techniques are necessary.
    Keywords: ddc:000
    Language: English
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  • 39
    Publication Date: 2014-02-26
    Description: The currently most efficient algorithm for inference with a probabilistic network builds upon a triangulation of a network's graph. In this paper, we show that pre-processing can help in finding good triangulations for probabilistic networks, that is, triangulations with a minimal maximum clique size. We provide a set of rules for stepwise reducing a graph, without losing optimality. This reduction allows us to solve the triangulation problem on a smaller graph. From the smaller graph's triangulation, a triangulation of the original graph is obtained by reversing the reduction steps. Our experimental results show that the graphs of some well-known real-life probabilistic networks can be triangulated optimally just by preprocessing; for other networks, huge reductions in their graph's size are obtained.
    Keywords: ddc:000
    Language: English
    Type: reportzib , doc-type:preprint
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  • 40
    Publication Date: 2014-11-11
    Description: {\begin{rawhtml} 〈a href="http://dx.doi.org/10.1007/s10479-007-0178-0"〉 Revised Version unter http://dx.doi.org/10.1007/s10479-007-0178-0〈/a〉 \end{rawhtml}} Wireless communication is used in many different situations such as mobile telephony, radio and TV broadcasting, satellite communication, and military operations. In each of these situations a frequency assignment problem arises with application specific characteristics. Researchers have developed different modelling ideas for each of the features of the problem, such as the handling of interference among radio signals, the availability of frequencies, and the optimization criterion. This survey gives an overview of the models and methods that the literature provides on the topic. We present a broad description of the practical settings in which frequency assignment is applied. We also present a classification of the different models and formulations described in the literature, such that the common features of the models are emphasized. The solution methods are divided in two parts. Optimization and lower bounding techniques on the one hand, and heuristic search techniques on the other hand. The literature is classified according to the used methods. Again, we emphasize the common features, used in the different papers. The quality of the solution methods is compared, whenever possible, on publicly available benchmark instances.
    Keywords: ddc:000
    Language: English
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  • 41
    facet.materialart.
    Unknown
    Publication Date: 2014-02-26
    Description: Telota ist ein Kunstwort, das für alle Aktivitäten der Berlin-Brandenburgischen Akademie der Wissenschaften steht, die der Förderung von Forschung, Kommunikation und Präsentation durch elektronische Medien dienen. In diesem Artikel werden die Entstehung des Telota-Projektes geschildert und die Ziele diskutiert, die mit diesem Projekt erreicht werden sollen. Es geht darum, moderne Informationstechnik bewusst, geplant und nachhaltig für alle Belange der {\rm BBAW} einzusetzen. Informationstechnische Werkzeuge sollen für die wissenschaftliche Arbeit effizient genutzt werden; die Information nach innen und nach außen soll deutlich verbessert werden; eine bessere Kommunikationsinfrastuktur soll die Zusammenarbeit fördern.
    Keywords: ddc:000
    Language: German
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  • 42
    Publication Date: 2022-07-07
    Description: The pole condition is a general concept for the theoretical analysis and the numerical solution of a variety of wave propagation problems. It says that the Laplace transform of the physical solution in radial direction has no poles in the lower complex half-plane. In the present paper we show that for the Helmholtz equation with a radially symmetric potential the pole condition is equivalent to Sommerfeld's radiation condition. Moreover, a new representation formula based on the pole condition is derived and used to prove existence, uniqueness and asymptotic properties of solutions. This lays the foundations of a promising new algorithm to solve time-harmonic scattering problems numerically and provides a new approach for analyzing existing algorithms such as the Perfectly Matched Layer (PML) method and the Bayliss-Gunzburger-Turkel (BGT) algorithm.
    Keywords: ddc:000
    Language: English
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  • 43
    Publication Date: 2022-07-07
    Description: In this paper we study the PML method for Helmholtz-type scattering problems with radially symmetric potential. The PML method consists in surrounding the computational domain by a \textbf{P}erfectly \textbf{M}atched sponge \textbf{L}ayer. We prove that the approximate solution obtained by the PML method converges exponentially fast to the true solution in the computational domain as the thickness of the sponge layer tends to infinity. This is a generalization of results by Lassas and Somersalo based on boundary integral eqaution techniques. Here we use techniques based on the pole condition instead. This makes it possible to treat problems without an explicitly known fundamental solution.
    Keywords: ddc:000
    Language: English
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  • 44
    ISSN: 1434-193X
    Keywords: Triplet recombination ; Electron transfer ; Radical ions ; Photochemistry ; Terpenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The triphenypyrylium tetrafluoroborate (TPT)-sensitized reactions of several terpene donor molecules, including sabinene (1), α-phellandrene (4), α-terpinene (5) and γ-terpinene (6) give rise to significantly different products than reactions induced by other electron-transfer sensitizers, such as 1,4-dicyanobenzene (DCB). The divergent reactions require decidedly different key intermediates; the products obtained with TPT can be explained by dissociative recombination of the intermediate radical-radical cation pair in the triplet state, generating donor-derived biradicals.
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  • 45
    ISSN: 1434-193X
    Keywords: Azides ; Cleavage reactions ; Cycloadditions ; Nitrogen heterocycles ; Polycycles ; Ring expansion ; Synthetic methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---2-Alkyl-1-methylquinazolinium hexafluorophosphates 9 are deprotonated by sodium or potassium hydride to afford solutions of 2-alkylidenedihydroquinazolines 10, which were investigated by NMR spectroscopy. Trapping with methanesulfonyl azide (5a) of 10 in situ or subsequent treatment with trifluoromethanesulfonyl azide (5b) gives mixtures of colourless (15) and intensely yellow N-sulfonylimino-1,4-benzodiazepines 16 along with products due to cleavage of the exocyclic double bond of 10, viz. 11 and 13. The ethylidene compound 10b yields the bicyclic products 18 and 19, apparently by complex sequences of reactions that are triggered by removal of the acidic proton at C-2 of 16b and 16f. The structures of the products are based on spectroscopic evidence and X-ray diffraction analyses performed on 15b, 16d, 16e, and 19.
    Additional Material: 6 Ill.
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  • 46
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1589-1593 
    ISSN: 1434-193X
    Keywords: Azaallenium ions ; Azaallylium ions ; Iminium ion ; Kinetics ; Linear Free Energy Relationships ; Ab initio calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The rate constants for the reactions of the 2-azaallenium ion 1b+, the 2-azaallylium ion 2a+ and the iminium ion 3+ with different nucleophiles were determined by 1H NMR spectroscopy. By correlation with the Linear Free Enthalpy Relationship (LFER) lg k20°C = s (E + N), developed by Mayr and Patz, the electrophilicity parameters E(1b+) = -3.7, E(2a+) ≍ -16 and E(3+) = -10.43 were obtained. They show that the relative reactivities of these ions are approximately 1012:1:106. Quantum chemical calculations (ab initio, DFT) of the methyl anion affinities for the ions 1b+,2a+ and3+ are in agreement with the experimental E values. The X-ray structure of 3+·CF3SO3- is reported for the first time; it shows no strong interaction between the cation and the anion.
    Additional Material: 2 Ill.
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  • 47
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1595-1601 
    ISSN: 1434-193X
    Keywords: Oxazoline N-oxide ; Cycloadditions ; Cycloadditions ; Lactams ; Thienamycin ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---[3+2] Cycloaddition between a camphor-derived oxazoline N-oxide 9 and the γ,δ-unsaturated enamino ester 11 afforded the single adduct 6. A stereoselective reduction of the enamino ester side chain allowed the control of the absolute configuration of the two additional asymmetric centres. Nitrogen protection and oxidative hydrolysis of the resulting product 13, followed by further functional group manipulations, led to the β-lactam derivative 1, a known precursor of the β-methylthienamycin derivative2a.
    Additional Material: 1 Ill.
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  • 48
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1603-1607 
    ISSN: 1434-193X
    Keywords: Boron ; Cyclotrimerizations ; Nitrogen heterocycles ; Macrocycles ; Subphthalocyanines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The regioselective preparation of ortho-substituted subphthalocyanides was achieved employing 3-substituted phthalonitrile derivatives as starting materials. A mechanistic proposal has been outlined.Supporting information for this article is available on the WWW under //http://www.wiley-vch.de/contents/jc_2046/2000/99525_s.pdf or from the author.
    Additional Material: 2 Ill.
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  • 49
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1609-1615 
    ISSN: 1434-193X
    Keywords: Terpenoids ; Natural products ; Total synthesis ; Cyclizations ; Rearrangements ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A new route for the synthesis of 2,7- and 7-functionalized labdanes starts from (R)-carvone (1). 11-Nordrim-7-en-9-one (15) is an appropriate starting material for the total synthesis of hispanone (21), a biologically active furolabdane isolated from the Mediterranean medicinal plant Ballota saxatilis.
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  • 50
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1623-1626 
    ISSN: 1434-193X
    Keywords: Iridoid glucoside ; (8S)-Kingiside ; (8S)-Loganin ; (8S)-7-Ketologanin ; Asymmetric synthesis ; Natural products ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The tetraacetyl derivative 8 of the naturally occurring kingiside (8a) was prepared from aucubin (1). Intermediates in the synthesis were (8S)-tetraacetyl loganin (6) and (8S)-tetraacetyl-7-ketologanin (7), whose free (8R)-epimers occur in many different plants (Caprifoliaceae, Loganiaceae). The 13C NMR spectrum allows the structure to be unequivocally identified.
    Additional Material: 1 Tab.
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  • 51
    ISSN: 1434-193X
    Keywords: Tetrakis(dimethylamino)naphthalenes ; Basicity ; Hydrogen bonds ; Cyclicvoltammetry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---For comparison to the recently described 2,3,6,7-tetrakis(dimethylamino)naphthalene (1) the three isomers 2,3, and 4 were synthesized. The basicities of this group of isomers are strongly dependent upon the different mutual orientations of the pairs of dimethylamino substituents: only the isomers 3 and, partially, 4, both with dimethylamino groups in adjacent peri-positions of the naphthalene, are strong “proton sponges”. For the isomers 1 and 2 with the same number and kind of twofold dimethylamino substituents in neighbouring ortho-positions, however, no significant basicity increase is observed. To explain this difference between the two groups of isomers it is suggested that in the ortho-pairs of 1 and 2 the C-N bonds diverge considerably, leading to an increased N···N distance and consequently to less stable [N···H···N]+ hydrogen bonds in contrast to the parallel C-N bonds in the peri-substituted isomers 3 and 4. X-ray crystal structure analyses of the bases and of some of the salts derived therefrom were solved and are discussed. Cyclic voltammetry indicates that 1 to 4 are strong electron donors, reacting easily to radical cations or dications which with suitable acids have been obtained as salts.
    Additional Material: 3 Ill.
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  • 52
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1677-1683 
    ISSN: 1434-193X
    Keywords: Radicals ; Cyclizations ; Pyridinethione ; Tetrahydrofurans ; Asymmetric synthesis ; Thiazolethione ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The trisubstituted functionalized tetrahydrofurans 10, 11, 16, 18, and 19 were photochemically prepared from 2,3-syn- and 2,3-anti-configuredN-(3-benzoyloxy-5-hexen-2-oxy)thiazole-2(3H)-thione anti-6, pyridinethiones 7, anti-8, and BrCCl3. The formation of tetrahydrofurans was achieved by an efficient and highly regioselective alkoxyl radical cyclization (5-exo-trig). The 2,3-anti substituted intermediates 9 and 12 cyclize stereoselectively whereas a 2,3-syn-configured O-radical affords both possible diastereomeric addition products in equal amounts. The cyclized tetrahydrofuryl methyl radicals were trapped with the bromine atom donor BrCCl3 to afford the bromomethyl-substituted cyclic ethers 10, 11, 18, and 19 in excellent yields. The utility of this reaction was stressed by conversion of one of the newly prepared tetrahydrofurans in a two-step synthesis into (+)-allo-muscarine (+)-20.Supporting information for this article is available on the WWW under //http://www.wiley-vch.de/contents/jc_2046/2000/99590_s.pdf or from the author.
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  • 53
    ISSN: 1434-193X
    Keywords: Thioketones ; Thiocarbonyl ylides ; Cycloadditions ; Cycloreversions ; Sulfur heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Reactions of diaryl thioketones with diazomethane at room temperature afford 4,4,5,5-tetraaryl-1,3-dithiolanes; the scope of this surprising 2:1 interaction has been studied for decades (Schönberg Reaction). The clue to the mechanism was our observation that the stoichiometry is 1:1 at -78 °C, and 2,5-dihydro-2,2-diaryl-1,3,4-thiadiazoles are formed as primary [2+3] cycloadducts. They lose N2 at -45 °C in first-order reactions generating diaryl thioketone S-methylides which can be intercepted by thioketones (→1,3-dithiolanes), multiple CC bonds, or acids HX. In the absence of trapping reagents, the elusive intermediates either dimerize furnishing 2,2,3,3-tetraaryl-1,4-dithianes or give rise to 2,2-diarylthiiranes by electrocyclization. Beyond thiobenzophenone and diazomethane, our main model reaction, the studies involve fluorene-9-thione, 4,4-dimethoxy- and 4,4-dichlorothiobenzophenone. The ring of 2,5-dihydro-2,2-diphenyl-1,3,4-thiadiazole (8) is opened by LDA at -78 °C and derivatives of anion 12 are obtained. - In summa: The Schönberg reaction consists of two 1,3-dipolar cycloadditions, linked by a 1,3-dipolar cycloreversion.
    Additional Material: 1 Ill.
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  • 54
    ISSN: 1434-193X
    Keywords: Conjugation ; Boron ; Sensors ; Cyclic voltammetry ; Polymers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---New electropolymerizable aromatic compounds (i.e. pyrrole, thiophene, aniline) bearing boronic acid and ester substituents have been synthesized and their electrochemical behavior has been investigated. Functionalized polythiophene and polypyrrole films could be anodically generated in acetonitrile, whereas the polyaniline derivative was electroformed in an acidic aqueous solution. The electrochemical responses of some of these materials were changed when fluoride ions were added to the electrolytic solutions. The strongest modifications, caused by binding of fluoride by the immobilized boron, were observed for the polypyrrole derivative in hydroorganic media.
    Additional Material: 5 Ill.
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  • 55
    ISSN: 1434-193X
    Keywords: Heterocycles ; Zinc ; Palladium ; Catalysts ; Sulfur ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Organozinc halides derived from Grignard reagents behave differently in their reaction with ethyl (±±)-(2RS,3SR)-tetrahydro-4-methylene-2-phenyl-3-(phenylsulfonyl)furan-3-carboxylate (3) according to the hybridisation of the carbon ligand. During the development of short multi-component reactions for the synthesis of diverse functionalized ethyl 2,5-dihydrofuran-3-carboxylates it was discovered that aryl and vinyl zinc halides undergo clean reaction with 3 in the presence of Pd(PPh3)4. In contrast, when alkyl zinc halides are reacted with 3 in the presence of Pd(PPh3)4, reductive desulfonation of 3 is observed. Remarkably, in the absence of a transition metal catalyst, the allylic substitution of 3 with alkyl zinc halides proceeds cleanly and in moderate to good yield.
    Additional Material: 2 Ill.
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  • 56
    ISSN: 1434-193X
    Keywords: Self-assembly ; Vapor-pressure osmometry ; Resorcin[4]arenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Resorcin[4]arene tetracarboxylic acids 5,6 (A) and resorcin[4]arene tetrapyridines 2,3 (P) self-assemble in chloroform solution to form stable heterotopic AP dimers. Data from NMR titration and dilution experiments, as well as from vapor-pressure osmometry (VPO), indicate that the AP dimer is formed with an association constant greater than 107 M-1. Solid-solution extraction experiments are indicative of the formation of a 2:1 trimer (A2P), while self-associated homotopic species (A2 and A3) can be detected by NMR and VPO. Analysis of the heterotopic noncovalent assembly process over a range of compositions shows that these other species are much less stable than the AP heterodimer, which is the exclusive species at an A/P concentration ratio of 1:1 (〉 99.7% of the total at 10 mM).
    Additional Material: 6 Ill.
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  • 57
    ISSN: 1434-193X
    Keywords: Sulfoxides ; β-Amino sulfones ; Mannich type reaction ; Lithium perchlorate ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The LiClO4-mediated one-pot reaction of aldehydes with (trimethylsilyl)dialkyl amines and the lithium salt of sulfoxides or sulfones, affords the corresponding β-(dialkylamino) sulfoxides and β-(dialkylamino) sulfones in high yields. The aminosulfoxidation reaction of aliphatic or aromatic aldehydes lacks diastereoselectivity, but the diastereomeric sulfoxides can be separated by HPLC or column chromatography for further use.
    Additional Material: 1 Ill.
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  • 58
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1741-1744 
    ISSN: 1434-193X
    Keywords: Bridged pyranose derivatives ; Ring enlargement ; Carbenes ; Glycosides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Addition of dichlorocarbene to the glycal (±±)-2 followed by cyclopropyl-allyl rearrangement leads to the chloro-2H-pyran (±±)-4. Oxidation of (±±)-4 and reduction of the obtained hydroxypyranone (±±)-5 gave the methyl pyranoside (±±)-6. The relative configuration of (±±)-6 was established by X-ray structural analysis of the corresponding acetate (±±)-7. The synthesis of the optically active starting materials (+)-2 and (-)-2 is also reported.
    Additional Material: 1 Ill.
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  • 59
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1745-1758 
    ISSN: 1434-193X
    Keywords: CMP-Neu5Ac analogues ; Enzyme inhibitors ; Substrate analogues ; Transition state analogues ; Transferases ; Carbohydrates ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Quinic acid was transformed into phosphitamides 16, 25, and 36, which could be readily linked to 5′-O-unprotected cytidine derivative 17. Ensuing oxidation of the obtained phosphite triesters with tBuO2H and hydrogenolytic de-O-benzylation furnished the corresponding phosphate diesters 18, 26, and 38. Base catalyzed removal of acetyl protecting groups, and methyl ester hydrolysis furnished CMP-Neu5Ac analogues 1d, 1e, and 2. Quinic acid was also transformed into 1,2-unsaturated diallyl α-hydroxymethyl-phosphate derivatives (R)- and (S)-46, which on reaction with cytidine phosphitamide 47 afforded the phosphite triesters. Subsequent oxidation with tBuO2H and then treatment with NEt3 gave phosphate diester derivatives (R)- and (S)-48. Deallylation, acetyl group removal, and methyl ester hydrolysis furnished (R)- and (S)-3, respectively. Treatment of (R)- and (S)-48 with DBU as a base led to acetic acid elimination, thus yielding, after de-O-allylation, acetyl group cleavage, and ester hydrolysis, diene derivative (E)-4. Donor substrate analogues 1d and 1e exhibited good α(2-6)-sialyltransferase inhibition (Ki: 2.0·10-4 and 2.0·10-5 M). However, transition state analogues (R)-, and particularly (S)-3 showed excellent inhibition properties (Ki: 1.6·10-6 and 2.7·10-7 M).
    Additional Material: 1 Tab.
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  • 60
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1759-1765 
    ISSN: 1434-193X
    Keywords: Cyclitols ; Aminocyclitols ; Glycosidase inhibitors ; α-Mannosidase inhibitors ; Deoxygenation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Three deoxy derivatives 2-4 of the α-mannosidase inhibitor mannostatin A (1) were synthesized, and their inhibition of Jack bean α-mannosidase was evaluated in order to elucidate the roles of each of the three hydroxyl groups of the inhibitor. The 1- and 2-deoxy derivatives 2 and 3 retained some inhibitory activity, although reduced by a factor of about 100 relative to the parent, whereas it was completely lost with the 3-deoxy derivative 4. Structure and activity relationships are discussed in the light of these findings.
    Additional Material: 1 Tab.
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  • 61
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1767-1772 
    ISSN: 1434-193X
    Keywords: Circular dichroism ; Conformation analysis ; s-Triazines ; Chiral auxiliaries ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---CD data of the optically pure 2-[(R)-1-(9-anthryl)ethylamino]-4-chloro-6-[(R)-1-(1-naphthyl)ethylamino]-1,3,5-triazine, 2[(R)-1-(9-anthryl)ethylamino]-4,6-bis[(R)-1-(1-naphthyl)ethylamino]-1,3,5-triazine, 2,4-bis[(R)-1-(9-anthryl)ethylamino]-6-chloro-1,3,5-triazine are presented. The analysis of the CD spectra by means of the nonempirical DeVoe approach has afforded the complete conformational characterisation of the three s-triazine derivatives, allowing us to establish how the conformation of these derivatives depends on the nature of the substituent 1-arylethylamino groups.
    Additional Material: 6 Ill.
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  • 62
    ISSN: 1434-193X
    Keywords: Cycloadditions ; Carbenes ; Nitrones ; Nitrilimines ; Pyrazolines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The reaction of tert-butylalkynyl chromium Fischer carbene complex 1 with nitrones 2 affords β-enamino-ketoaldehydes 4 by the light-promoted rearrangement of the corresponding [3+2] cycloadduct carbene complexes 3. On the other hand, [3+2] cycloaddition of chiral nonracemic Fischer alkenyl carbene complexes 19 with nitrilimines 10 yields enantiomerically pure Δ2-pyrazolines with high regio- and diastereoselectivity.
    Additional Material: 3 Ill.
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  • 63
    ISSN: 1434-193X
    Keywords: Asymmetric synthesis ; Zinc ; Transition structures ; QM/MM computations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Trimethylsilyl substitutions of the fenchyl alcohols [(1R,2R,4S)-exo-(2-Ar)-1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol, Ar = 2-methoxyphenyl (1) and Ar = 2-(dimethylaminomethyl)phenyl (2)] yield the chiral ligands 3 [Ar = 2-methoxy-3-(trimethylsilyl)phenyl] and 4 [Ar = 2-(dimethylaminomethyl)3-(trimethylsilyl)phenyl]. Increased reactivities and enantioselectivities in diethylzinc additions to benzaldehyde are obtained from 3 (63% ee R) and 4 (93% ee S), relative to 1 (26% ee S) and 2 (73% ee S). X-ray crystal structures of 3 and of its methylzinc complex 3-Zn reveal out-of-plane bending of the methoxy groups as major geometrical consequences of the trimethylsilyl substitutions. Analyses of QM/MM ONIOM μ-O transition-structure models for 1, 2, 3, and 4 show that trimethylsilyl-induced distortions of methoxy and of dimethylaminomethyl groups explain the observed increased enantioselectivities.
    Additional Material: 10 Ill.
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  • 64
    ISSN: 1434-193X
    Keywords: Palladium ; exo-π-Allylpalladium complexes ; Allylic alkylation ; Spiro compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The palladium(0)-catalyzed alkylation of 2,3-bis(acetoxymethyl)bicyclo[2.2.1]hepta-2,5-diene 1 with malonate-type enolates as nucleophiles is investigated. A monoalkylated product is formed first, and undergoes (depending on the nucleophile used) a second intramolecular reaction leading to spirocyclopropane-annulated bicyclo[2.2.1]heptene derivatives 5. The formation of endo spirobicyclic cyclopropanes adducts as major isomer is rationalized by assuming formation of an intermediate exo-(π-allyl)palladium complex.
    Additional Material: 2 Ill.
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  • 65
    ISSN: 1434-193X
    Keywords: Ketones ; Reductions ; Micelles ; Cobalt ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Operationally simple and environmentally benign procedures have been developed to selectively reduce different α,β-unsaturated ketones, 4,4-dimethylcyclohex-2-ene-1-one (1), isophorone (2), benzylideneacetone (3), chalcone (4) by NaBH4 or by the system NaBH4 + CoCl2. Alternative reaction media to the extensively used MeOH have been explored, and new procedures take advantage of the acceleration and chemoselectivity induced by water or by aqueous micellar solutions. It was possible to selectively and quantitatively afford pure products of 1,2 and of 1,4 reduction as well as the totally reduced compounds (yield and selectivity 〉 90%) by simple changes in the experimental conditions.
    Additional Material: 4 Ill.
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  • 66
    ISSN: 1434-193X
    Keywords: C-Glycosides ; Conformation analysis ; Molecular dynamics ; Selectins ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The conformational behavior of the C-glycosyl analogue of sialyl-α-(2→3)-galactose, synthesized as a glycosidase inhibitor, has been studied using a combination of NMR spectroscopy (J and NOE data) and molecular dynamics calculations. The obtained results show that the population distribution of conformers with respect to the orientation about the pseudo-glycosidic linkages is mainly controlled by steric interactions. This is in contrast to findings made for O-glycosides. In these natural compounds, the conformational behavior about the glycosidic linkage Φ is mainly governed by the exo-anomeric effect.
    Additional Material: 5 Ill.
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  • 67
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1815-1820 
    ISSN: 1434-193X
    Keywords: Asymmetric synthesis ; Palladium-catalysed couplings ; Palladacycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Chiral C2-symmetric N-benzylazetidines have been conveniently prepared from optically pure anti-1,3-diols without loss of enantiomeric purity. N-Debenzylation led to the corresponding N-unsubstituted azetidines, which were then subjected to palladium-catalysed coupling reactions with aryl bromides to afford chiral N-arylazetidines. (R,R)-N-Benzyl-2,4-dimethylazetidine has been employed in the synthesis of a new cyclopalladated complex, which can be used, for instance, as a chiral recognition agent for phosphorus ligands.
    Additional Material: 1 Tab.
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  • 68
    ISSN: 1434-193X
    Keywords: Cyclizations ; Spiro compounds ; Nucleosides ; Isomerizations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Syntheses of the spiro nucleosides 2′-deoxyhydantocidin 3a and its 1′-epimer 3b are described. The newly developed route involves a Horner-Wadsworth-Emmons condensation of the phosphonate 16 with the erythrose derivative 15 affording a mixture of six isomers which was fully assigned by NMR spectroscopy. The mixture was directly converted into the final compounds in an efficient base-catalyzed cyclization reaction. A base-catalyzed interconversion between the two isomers was observed.
    Additional Material: 2 Ill.
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  • 69
    ISSN: 1434-193X
    Keywords: Benzodiazepines ; Heterocycles ; Azeto[1,2-a]-1,5-benzodiazepines ; Cyclizations ; Cycloadditions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The reaction of o-phenylenediamine (4) with one, two or three equivalents of p-substituted 3-dimethylaminopropiophenone hydrochlorides 5a-e was studied. 4-Aryl-2,3-dihydro-1H-1,5-benzodiazepine derivatives 6a-e were obtained in good yields, along with the 1:2-adducts 7c-e and the unexpected 1:3-adducts rac-8c-e. The type of adduct formed is determined by the molar ratio of the reactants 4 and 5 and by the nature of the substituent in the para position of the propiophenone 5.
    Additional Material: 1 Ill.
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  • 70
    ISSN: 1434-193X
    Keywords: Cup-shaped PAHs ; Host-guest compounds ; Host-guest chemistry ; Cyclizations ; Semiempirical calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Cyclotrimerisation of benzo-polycyclic bromostannylalkenes 8a-d with Cu(NO3)2·3H2O in THF affords benzotri(benzonorbornadienes) 3a-d as a mixture of the syn and anti isomers. The ratio of syn to anti is close to the 1:3 statistical value in most cases (i.e. in cyclotrimers 3a,b,d), but highly in favour of the anti isomer in 3c, where steric hindrance by the methoxy groups plays an important role in the stereochemistry of the cyclotrimerisation. The substrates for the cyclotrimerisation, i.e. the bromostannyl alkenes 8a-d, were prepared from bromoalkenes 7a-d by treatment with base (LDA) and quenching with trimethyltin chloride. In turn, bromoalkenes 7a-d were prepared from alkenes 5a-d by radical bromination-elimination. The reaction conditions used were designed to minimise Wagner-Meerwein rearrangements that would lead to unwanted bromo isomers. The cup-shaped syn cyclotrimers 3a-d exhibit high electron density within the cavity as determined by AM1 semiempirical calculations of their electrostatic potential surfaces and are valuable substrates for supramolecular chemistry. As an example, it is shown that fullerene C60 is drawn into solution in acetonitrile by complexation with both the syn and anti trimer of benzonorbornadiene 3a.
    Additional Material: 1 Tab.
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  • 71
    ISSN: 1434-193X
    Keywords: Carbene complexes ; Enamines ; Metallatrienes ; Cyclopentadienes ; Dihydropyrroles ; spiro-Tetrahydropyrroles ; Iminium carbonylmetalates ; Dimetallapolyenes ; Tungsten ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Reactions of the [(1-alkynyl)carbene]tungsten complex (CO)5W=C(OEt)C≡CPh (1) with 1-aminocyclohexenes 2a-c and 7a-c afford different types of products depending on the amino substituents and the reaction conditions. (4-Aminocyclobutenyl)carbene complexes B have been shown to be generated in the first reaction step through a [2+2] cycloaddition. These are key intermediates and afford cross-conjugated tungstatrienes E, (conjugated) 1-tungsta-1,3,5-hexatrienes G, or (non-conjugated) 1-tungsta-1,3,6-heptatrienes F by following competing reaction pathways. Cross-conjugated 1-tungstatrienes 3 have been isolated in 52-74% yield by performing the reactions of 1-aminobenzocyclohexenes 2a-c with compound 1 in pentane. In dichloromethane instead of pentane, (conjugated) 1-tungsta-1,3,5-hexatrienes 4 are obtained, which subse-quently undergo fragmentation to give cyclopentadienes 6 (by π-cyclization) and dihydropyrroles (by α-cyclization) in a molar ratio dependent on the nature of the amino substituents. (Non-conjugated) 1-tungsta-1,3,6-heptatrienes 10 are generated upon reaction of 1-aminocyclohexenes 7a-c with compounds 1, which are transformed into cyclopentadienes 12 via conjugated 1-tungsta-1,3,5-hexatrienes 9 as intermediates. Reactions of 1-tungsta-1,3,6-heptatrienes 10 with the (1-alkynyl)carbene complex 1 afford dinuclear compounds 14, which subsequently yield indenes 15 (by two successive π-cyclization steps) and spiro-tetrahydropyrroles 16 (by both a π-cyclization and an α-cyclization step), depending on the steric bulk of the amino substituent.
    Additional Material: 3 Ill.
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  • 72
    ISSN: 1434-193X
    Keywords: Allyl alcohols ; Organocerium reagents ; Alkenes ; Addition reactions ; Cerium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Alkylcerium reagents add to the multiple bonds of allyl and propargyl alcohols in good yields and under mild conditions. The double bond can be reduced with lithium aluminum hydride in the presence of cerium trichloride. The regiochemistry of the attack depends on electronic factors.
    Additional Material: 1 Tab.
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  • 73
    ISSN: 1434-193X
    Keywords: Amidines ; Chiral bases ; N-Acyliminium ions ; Enantioselective catalysis ; Chiral pool ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The synthesis of four enantiopure hydroxyamidines is described. One amidine was obtained from (S)-pyroglutamic acid. Its key step involved the addition of phenylmagnesium bromide to the corresponding ester, affording the tertiary alcohol without detectable racemization. The second amidine was obtained by coupling of an (S)-malic acid derived N-acyliminium ion with β-naphthol. The other amidines were obtained from an (S)-serine-derived imide which was reduced to two diastereomeric lactams that were eventually transformed into the corresponding amidines.
    Additional Material: 1 Ill.
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  • 74
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 155-163 
    ISSN: 1434-193X
    Keywords: Macrocycles ; Cyclizations ; Strained compounds ; Ketophosphonate ; Iodoalkyne ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Two strategies have been explored to build the highly strained eleven-membered ring 2, a potential precursor for the biosynthetic key intermediate of the protoilludane family: an intramolecular Horner-Wadsworth-Emmons olefination and an intramolecular Nozaki-Hiyama-Kishi type-ring closure.
    Additional Material: 4 Tab.
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  • 75
    ISSN: 1434-193X
    Keywords: Neutral anion receptor ; Hydrogen bonds ; Urea moieties ; Donor-acceptor systems ; Macrocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The synthesis of macrocyclic and acyclic cleft-like anion receptors in which four hydrogen bond donating urea moieties are present in a preorganized fashion is described. NMR spectroscopy shows the complex formation with H2PO4- and Cl -. Cleft-like receptors bind H2PO4- in a 2:1 guest-host stoichiometry (Ka = 107M-2) in DMSO, whereas Cl - is bound in a 1:1 stoichiometry (Ka = 103M-1). The macrocyclic receptors form a 1:1 complex with H2PO4- (Ka = 103M-1 in DMSO) with a 100-fold selectivity for H2PO4- over Cl -.
    Additional Material: 3 Ill.
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  • 76
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 193-198 
    ISSN: 1434-193X
    Keywords: Nucleophilic substitutions ; Azulenes ; Hydroxylation ; Amination ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Hydroxylation of azulenes with tert-butylhydroperoxide proceeds efficiently at the 6-position when the former contain electron-withdrawing substituents in the five-membered ring. Similarly, VNS amination of azulenes proceeds with 4-amino-1,2,4-triazole; its anion, being an active nucleophile, also reacts with unsubstituted azulene. A variety of transformations of 6-hydroxyazulenes, such as substitution of the corresponding sulfonates with nitrogen, oxygen, sulfur, carbon nucleophiles and halogens, and the Claisen rearrangement of allylic ethers, is reported.
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  • 77
    ISSN: 1434-193X
    Keywords: Heterocycles ; Carbohydrates ; Imidazolidines ; Oxazolidines ; Spiro compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Prochiral 1,3-dihydroxyacetone forms racemic oxazolidine- and oxazoline-type spiro[4.4]nonanes upon reactions with potassium (thio)cyanate and cyanamide. In contrast, 1,3-diaminoacetone yields only the corresponding spiro-bisimidazolidinethione under similar conditions together with monocyclic by-products, but the spiro-bisimidazolidinone is accessible by reaction of 1,3-dichloroacetone with urea. The resolution of the racemic spiro-bisoxazolidinethione 2a was achieved by using brucine as the resolving agent.
    Additional Material: 1 Ill.
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  • 78
    ISSN: 1434-193X
    Keywords: Homogeneous catalysis ; Palladium ; Acetoxylation ; Acryloxylation ; Addition reactions ; Cyclooctadiene ; Cyclooct-4-enone ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Palladium-catalyzed acryloxylation of several cycloalkenes in the presence of the Pd(OAc)2/p-benzoquinone/MnO2 catalytic system is reported. This oxidation reaction yields allylic acrylates as the sole products through the intermediacy of an η3-allyl complex. However, with 1,5-cyclooctadiene (3), cyclooct-4-enone (4) is the major reaction product. Its formation results from oxidation, which is also observed in the palladium-catalyzed acetoxylation of 3. It has been shown that this is the result of a 1,2-trans addition (acryloxy-palladation), followed by a β-hydride elimination, which yields an enol acrylate or acetate. A second Markovnikov-oriented 1,2-trans-acryloxy-palladation on the latter yields a palladium complex, rearrangement of which gives 4.
    Additional Material: 1 Ill.
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  • 79
    ISSN: 1434-193X
    Keywords: Amino acids ; coupling ; N-Substituted amide ; Cyclizations ; Cyclic dipeptides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A short synthesis of new, functionalized seven-membered ring cyclic dipeptides is described. After the coupling of N-protected β-amino acids to N-substituted α-amino tert-butyl esters, the protective groups of the terminal functions were removed and the cyclization took place diastereoselectively in the presence of the coupling agent BOP. Amide substitution was found to be effective in promoting the cyclization of linear dipeptides.
    Additional Material: 1 Ill.
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  • 80
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 275-280 
    ISSN: 1434-193X
    Keywords: Radical reactions ; Substituent effects ; Nitrogen heterocycles ; Dihydropyridines ; Pyrrolines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A set of allene-tethered benzoyloximes (5) has been treated with nBu3SnH. Depending on their substitution pattern, a wide range of compounds has been obtained. If the stannyl radical adds on the allene, the C-centred radical thus formed undergoes either a 5-exo ring closure to give the cyclopentene derivatives 7 or a 6-endo ring closure onto the N atom to give the dihydropyridines 8. If the stannyl radical adds on the benzoyl moiety, an iminyl radical is formed which leads to the 3H-pyrroles 9 and the alkylidene-pyrrolines 10. Steric effects as well as polar effects are the factors governing the reaction course.Supporting information for this article is available on the WWW under //http://www.wiley-vch.de/contents/jc_2046/2000/99373_s.pdf or from the author.
    Additional Material: 1 Ill.
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  • 81
    ISSN: 1434-193X
    Keywords: Antibiotics ; Configuration determination ; Heterocycles ; Hongoquercin A ; Terpenoids ; Total synthesis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---(±)-Hongoquercin A (1), the racemate of an antibacterial fungal metabolite, has been synthesized starting from geranylacetone (2) and ethyl orsellinate (ethyl 2,4-dihydroxy-6-methylbenzoate, 5). The structure (±)-1 has been confirmed by X-ray analysis of its ethyl ester (±)-10. Synthesis of the naturally occurring (+)-hongoquercin A from (-)-sclareol (11) established its configuration as depicted in 1.
    Additional Material: 1 Ill.
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  • 82
    ISSN: 1434-193X
    Keywords: Carbohydrates ; Amino sugars ; Protecting groups ; Glycosylations ; Trichloroacetimidates ; Oligosaccharides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The N-DMM-Protected lactosamine derivative 2 was readily transformed into the corresponding glycosyl donor 4 and into acceptor 5. A TMSOTf-catalyzed glycosidation afforded the derived tetrasaccharide 6 which led to glycosyl donor 9. Reaction of 9 with lactose derivative 10 as acceptor gave the desired hexasaccharide 11. Cleavage of all protective groups and N-acetylation afforded the target molecule 1b (lacto-N-neohexaose). Glycosylation of acceptor 10 with donor 4 furnished tetrasaccharide 16 which, employing standard procedures, gave acceptor 18. Glycosylation of 18 with donor 9 furnished, under standard conditions, octasaccharide 19. Cleavage of all protective groups and N-acetylation afforded the target molecule 1c (lacto-N-neooctaose). Both 1b and 1c were obtained in good overall yields.
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  • 83
    ISSN: 1434-193X
    Keywords: Sharpless asymmetric dihydroxylation ; Asimilobin ; Tetrahydrofuran ring ; Wittig reactions ; Annonaceous acetogenins ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The most efficient method for the synthesis of the trans/threo/trans-bis(tetrahydrofuran) (THF) ring unit was established, and the first total synthesis of (-)-asimilobin and its diastereomer was then accomplished in twelve and fourteen steps, respectively, from trans-1,5,9-decatriene, by a convergent route with a Wittig reaction as the key step. By virtue of these synthetic results, the absolute configuration of the bis(THF) unit in naturally occurring asimilobin should be corrected.
    Additional Material: 3 Ill.
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  • 84
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 381-385 
    ISSN: 1434-193X
    Keywords: Enynes ; Macrocycles ; Coordination chemistry ; Crown compounds ; Radicals ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The complex molecular structure and interesting activation mechanisms of naturally occurring enediynes have inspired the synthesis of a variety of simpler model systems to mimic their properties. While in most model compounds nucleophilic attack, isomerization or bioreduction are used to activate the unsaturated system for diradical cyclization, some attempts have been made to employ metal-ion coordination for this purpose. Significant enhancement of the thermal reactivity has been achieved by metal-ion induced conformational and electronic changes of suitably substituted enediynes, such as 1, 5, 6, 17 and 18. Enediyne activation by stoichiometric or catalytic formation of vinylidene complexes, such as 22, from terminal alkynes has also been investigated. This paper summarizes recent results pursuing the activation of enediyne diradical cyclization by metal ions.
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  • 85
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 419-423 
    ISSN: 1434-193X
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The first enantioselective synthesis of enantiomerically pure (-)-wine lactone, (-)-1a, a fragrance constituent of various white wines, and its epimer (+)-1b, was carried out. The key steps are allylic substitution of (±)-2-cyclohexen-1-yl acetate (2) with dimethylmalonate using palladium complexes of phosphanyldihydrooxazol L1 or of the phosphanylcarboxylic acid L2 as catalyst, subsequent decarboxylation, iodolactonization and elimination, furnishing enantiomerically pure bicyclic lactone (+)-7 in 47% overall yield. The diastereoselective introduction of methyl groups by SN2′-type substitution with an organocopper compound and by enolate alkylation gave lactone (-)-1a in 43% overall yield from (+)-7.
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  • 86
    ISSN: 1434-193X
    Keywords: Aplykurodins ; Marine steroids ; C-C coupling ; Cyclic peroxides ; Lactonization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---An approach to the synthesis of aplykurodins, ichthyotoxic marine lactones, is presented. The carbon framework was derived from vitamin D3 by conversion of the readily accessible allyl alcohol 13 to the protected Grundmann's hydroxy ketone 22 and subsequent introduction of the C2 side chain through a Pd0-promoted coupling. Highly stereoselective hetero Diels-Alder reaction with O21 produced the key intermediate peroxide 25. Functional group transformations, coupled with a series of chemo- and stereoselective reactions, finally resulted in the synthesis of the unnatural analogue 17,18-dihydro-3,9-di-epi-aplykurodinone B (6).
    Additional Material: 2 Ill.
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  • 87
    ISSN: 1434-193X
    Keywords: Zeolites ; Radical ions ; Ring opening ; Electron transfer ; Oxidations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Incorporation of trans-1,2-diphenylcyclopropane (1) and its 3,3-D2-isotopomer into the channels of a redox-active pentasil zeolite (Na-ZSM-5) resulted in the formation of exo,exo-1,3-diphenylallyl radical (2•) and its 2-D1 isotopomer, respectively. This conversion requires oxidation, ring opening, and deprotonation, in an unspecified sequence. The allyl radical 2• is also formed upon incorporation of trans-1,3-diphenylpropene (3). A comparison with the solution photochemistry, in the presence or absence of added base, shows the conversion of 1 into 2• to be a zeolite-specific reaction. Incorporation of arylcyclopropanes 9 (R = H, OCH3) into ZSM-5 generated trans-propenylbenzene radical cations 10•+ (R = H, OCH3); the 2,2-D2 isotopomer of 9 (R = OCH3) gave rise to three different isotopomers of 10•+ (R = OCH3).
    Additional Material: 2 Ill.
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  • 88
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 485-490 
    ISSN: 1434-193X
    Keywords: Calixarenes ; Tripodal cryptand ; Extraction abilities ; Cations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The tripodal calixcryptands have been one of the scarcely explored fields in calixarene chemistry due to the difficulties in their preparation. The strategy presented in this paper shows that novel tripodal calixcryptands can be conveniently prepared by directly treacing p-tert-butylcalix[n]arenes (n = 4, 6) with a multi-functional polypode reagent, e.g. 1,1,1-tris(tosyloxyethoxyethoxymethyl)propane or tetrakis(tosyloxyethoxyethoxymethyl)methane, under selected conditions. The first example of 1,2,4-tripodal calix[6]cryptands has been prepared. Novel calix[6]crown and doublecalix[4]arenes were co-prepared. The extraction abilities of these novel calixcryptands toward several alkali metal ions, ammonium and alkylammonium ions are presented.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 89
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 521-525 
    ISSN: 1434-193X
    Keywords: Allyl aryl sulfones ; Nitroarenes ; Condensation reaction ; Lewis acids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Allyl aryl sulfones 2 react with aryl nitrocompounds 1 in a DBU/MgCl2 system giving the 4-arylsulfonyl quinolines 3. Some mechanistic aspects of the reaction are discussed. Application of this reaction to the formal total synthesis of the natural product (-)Eupolauramine is described.
    Additional Material: 1 Tab.
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  • 90
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 527-538 
    ISSN: 1434-193X
    Keywords: Furans ; Pyrans ; Dihydropyran-2-ylidenes ; Ring closure ; Addition reaction ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---On treatment with base the pentynones 8a-f undergo anionic addition reactions of the resulting enolate species to the alkyne moiety and afford the 2,5-disubstituted furans 10a-f in yields ranging from 10-91%. The proposed mechanism involves the 2-methylene-dihydrofurans 11 as intermediates which tautomerize to yield the observed products. In the case of the α-picolyl derivative 8g both possible enolates 12 and 13 are formed which are subsequently transformed to the products 10g and 14g, respectively. Starting with the hexynones 9a-e an analogous reaction takes place with the formation of the pyran derivatives 15 and 16 in comparable yields. Under the same reaction conditions the n-butyl ketone 9f gives rise to two isomeric compounds, namely the 4H-pyran 16f and the cyclohexenone 17. This result is explained by assuming initial formation of two isomeric enolates which react either by O- or C-attack on the carbon-carbon triple bond.
    Additional Material: 5 Tab.
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  • 91
    ISSN: 1434-193X
    Keywords: Alkylations ; Deaminated AdoHcy ; Decarboxylated AdoHcy ; Mitsunobu reaction ; Nucleosides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---5′-Acetylthio-5′-deoxy-2′,3′-O-isopropylideneadenosine (8) was directly prepared from commercially available 2′,3′-O-isopropylideneadenosine (7) and thioacetic acid under Mitsunobu conditions in almost quantitative yield. In situ cleavage of the acetylthio function of 8 followed by coupling with different alkyl bromides proceeded with high yields. Deprotection of the obtained 5′-thionucleosides yielded the S-adenosyl-L-homocysteine analogues decarboxylated AdoHcy (11), deaminated AdoHcy (14) and 5′-[3-(cyano)propylthio]-5′-deoxyadenosine (16) in good overall yields. Direct deprotection of the thionucleoside 8 delivered 5′-thio-5′-deoxyadenosine (18) in excellent yield. In addition, binding constants of these AdoHcy analogues and the DNA methyltransferase M·HhaI were determined in a fluorescence assay.
    Additional Material: 1 Ill.
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  • 92
    ISSN: 1434-193X
    Keywords: Amino ketones ; Homogeneous catalysis ; Aziridination ; Copper ; Enols ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A series of acyclic and cyclic enol derivatives 1 has been transformed into the corresponding α-amino-functionalized ketones 2 by means of enantioselective catalytic aziridination with chiral Cu complexes, prepared in situ from [Cu(MeCN)4]PF6 and the optically active ligands 3, by using (N-tosylimino)iodobenzene (PhINTs) as a nitrogen source. The best enantioselectivities (ee values of up to 52%) have been achieved for the electronically deactivated enol acetate 1aδ, but the incorporation of steric bulk and the substitution pattern at the enol double bond do not improve the ee values. The cyclic substrates react considerably less readily (only up to 45% conversion) compared to their acyclic counterparts (complete consumption). A transition structure is suggested for the asymmetric Cu-catalyzed aziridination of the enol acetate 1aδ in the presence of the chiral ligand 3b that could account for the sense of the (R)-configured product 2a.
    Additional Material: 1 Ill.
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  • 93
    ISSN: 1434-193X
    Keywords: Porphyrins ; Chiral auxiliaries ; Macrocycles ; Pyrethroids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Esters, N,N-disubstituted amides, and a N-acylurea derived from the enantiopure industrial intermediate (1R)-cis-hemicaronaldehydic acid (or biocartol) are convenient synthons for the preparation of a series of chiroporphyrins by condensation with pyrrole. These chiral meso-tetracyclopropylporphyrins are obtained exclusively as the D2-symmetric α,β,α,β atropisomer, generally in low to moderate yields (2-20%), and in the urea case in excellent yield (60%). Hydrolysis of the urea substituents affords a chiroporphyrin with mono-N-substituted amide groups. 1H-NMR spectroscopy indicates that the ester, amide, and urea stereogenic groups sit on the porphyrin close to the metal binding site and restrict substrate or ligand access along a C2-symmetric groove. This structural feature of chiroporphyrins and of their metal complexes is of high potential interest in asymmetric catalysis and chiral recognition.
    Additional Material: 3 Ill.
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  • 94
    ISSN: 1434-193X
    Keywords: Cyclophanes ; Molecular recognition ; Molecular shuttles ; Rotaxanes ; Template-directed synthesis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Two dumbbell-shaped compounds (8 and 11), each composed of two polyether chains intercepted by a 1,4-dioxybenzene recognition site, terminated by tetraarylmethane-based stoppers, and emanating from a central 9,10- or a 2,6-dioxyanthracene unit, have been synthesized. Two [2]rotaxanes (9 · 4 PF6 and 12 · 4 PF6) have been prepared by interlocking these dumbbell-shaped compounds (8 and 11) with a bipyridinium-based tetracationic cyclophane (15 · 4 PF6) - namely, cyclobis(paraquat-p-phenylene). A [3]rotaxane (10 · 8 PF6) incorporating two cyclophane components (15 · 4 PF6) was also obtained when the 9,10-dioxyanthracene-containing dumbbell-shaped compound (8) incorporating two 1,4-dioxybenzene recognition sites was employed. The 1H-NMR spectroscopic investigation of the [2]rotaxanes (9 · 4 PF6 and 12 · 4PF6) revealed that the cyclophane component encircles one of the two 1,4-dioxybenzene recognition sites in the 9,10-dioxyanthracene-containing [2]rotaxane (9 · 4 PF6) and the 2,6-dioxyanthracene unit in the other [2]rotaxane (12 · 4 PF6). These structures have been confirmed by UV/Vis and electrochemical experiments. Comparison with the spectroscopic properties of simple model compounds shows the presence of electronic interactions which lead to (i) the occurrence of very efficient energy transfer processes in the dumbbell-shaped components and (ii) perturbations in the absorption spectra with appearance of two charge-transfer absorption bands and complete luminescence quenching in the [2]rotaxanes. For the 2,6-dioxyanthracene-containing [2]rotaxane (12 · 4 PF6), it has been demonstrated that the cyclophane can be displaced from the dioxyanthracene to the 1,4-dioxybenzene station upon electrochemical oxidation.
    Additional Material: 9 Ill.
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  • 95
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 627-631 
    ISSN: 1434-193X
    Keywords: Complex nucleoside ; Antibiotics ; Radicals ; Zn-Cu couple ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Homosinefungin 5, which can be considered as an analogue of S-adenosylmethionine (SAM) and of S-adenosylhomocysteine (SAH), has been synthesized by means of a sequence in which the key step was the addition of a radical, produced by the simple treatment of an iodide precursor with a zinc-copper couple, to suitably activated olefins.
    Additional Material: 1 Ill.
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  • 96
    ISSN: 1434-193X
    Keywords: Amide linkage ; Phosphodiester ; Hammerhead ribozyme ; Oligonucleotides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A nucleoside dimer in which the natural phosphodiester bond is replaced by an isosteric amide linkage has been prepared. This dimer analogue was subsequently incorporated chemically at the cleavage position of a hammerhead ribozyme substrate. Although the resulting substrate analogue exhibited a high affinity for the ribozyme as shown by gel retardation assays, the amide bond proved to be fully resistant to cleavage under standard conditions of ribozyme cleavage activity.
    Additional Material: 3 Ill.
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  • 97
    ISSN: 1434-193X
    Keywords: Solid-phase synthesis ; Wang resin ; Hetero Diels-Alder reactions ; Dihydropyrans ; Reductive reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The OH groups of Wang resin were esterified with benzylidenepyruvic acid (1) to give the immobilized 1-oxabutadiene 2. The latter reacted with vinyl ethers 3a-h (dienophiles) in the presence of Eu(fod)3, and the resulting adducts 4a-h underwent reductive cleavage with LiAlH4 to afford the dihydropyrans 5a-h in high (62 to 100%) overall yields. A similar sequence carried out under conventional homogeneous liquid phase conditions led to significantly lower yields. The endo/exo selectivity of the cycloaddition reaction was the same in both cases.
    Additional Material: 2 Tab.
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  • 98
    ISSN: 1434-193X
    Keywords: Cationic amphiphiles ; Transfection ; Pyridinium salts ; Vesicles ; Lipoplex ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Pyridinium amphiphiles have found practical use for the delivery of DNA into cells. Starting from 4-methylpyridine, a general synthesis has been devised for the production of pyridinium amphiphiles which allows variation in both the hydrophobic part and in the headgroup area of the compounds. By means of differential scanning microcalorimetry, zeta potential, particle size measurements and cryo electron microscopy, some characteristics of the pyridinium amphiphile/DNA complexes have been determined.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 99
    ISSN: 1434-193X
    Keywords: Pauson-Khand reaction ; Cyclopentenones ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---1-Methyl-norbornene ester 9 and 1-methyl-2,3-diazabicyclo[2.2.1]heptene ester 10 were employed in intermolecular Pauson-Khand reactions with various terminal alkynes 11a-f to give the dimethyl 1-methyltricyclo[5.2.1.05,9]dec-7-en-6-one 2,3-dicarboxylates 12 and 13, and diethyl 2,3-diaza-1-methyltricyclo[5.2.1.05,9]dec-7-en-6-one 2,3-dicarboxylates 14 and 15, respectively. Whereas the co-cyclization of norbornene 9 with alkynes 11 bearing small substituents R resulted in the preferred formation of 12 (12:13 ≤ 85:15), regioisomer 13 was obtained as the major product when sterically bulky alkynes were employed (12:13 ≥ 6:94). For 2-methyl-3-butyn-2-ol 11e a strong temperature dependency of the regioselectivity was found. The ratio of regioisomers (12e:13e) changed from 95:5 at -25 °C to 12:88 at 120 °C in toluene. In contrast, reactions with 2,3-diazanorbornene 10 showed only moderate regioselectivities in favour of 14 (14:15 ≤ 69:31), regardless of the temperature and the size of R. The observed regioselectivities support a mechanism for the Pauson-Khand reaction in which the apical rather than the basal anti oriented carbon monoxide ligand of cobalt alkyne complex 1 is replaced by the alkene.
    Additional Material: 1 Ill.
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  • 100
    ISSN: 1434-193X
    Keywords: Reverse-turn mimics ; γ-Turns ; β-Turns ; β-Hairpins ; Peptides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Conformational analysis of N-acetylated hexapeptide mimics incorporating a bicyclic lactam (1-4) was carried out by a combination of 1H-NMR spectroscopy, IR spectroscopy, and computer modeling. The nature of the bicyclic lactam determines the turn motifs and the folding patterns of these constrained peptides. The (5,6)-bicyclic lactam derivatives 1 and 2, characterized by a type-II' β-turn (C=O3···H6-N), are very compact intramolecularly H-bonded structures. The (5,7)-bicyclic lactam derivative 3, characterized by an inverse γ-turn (C=O4···H6-N), is a quite flexible “tweezer-like” structure.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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