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  • ddc:004
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  • 1
    Publication Date: 2020-12-11
    Description: Im Mai 2009 wurde Wolfram|Alpha gestartet, ein Service, der seinen Namen von seinem Entwickler, dem britischen Mathematiker Stephen Wolfram, ableitet. Dem Benutzer soll nicht nur eine Liste von Webseiten als Ergebnis auf Anfragen geliefert werden, sondern Antworten auf konkrete Fragen geben. In diesem Report soll gezeigt werden, warum sichWolframjAlpha von Suchmaschinen abgrenzt und was die Berechnung von Antworten auf natürlichsprachliche Fragen möglich machen kann.
    Description: Wolfram|Alpha was started in May 2009 and it's a service whose name derives from the british mathematician Stephen wolfram. As a result for a request the user is not just supported with a list of websites but with answers for concrete questions. In this report it will be shown why Wolfram|Alpha seperates from search engines and moreover what makes the computation of answers for natural language queries possible.
    Keywords: ddc:004
    Language: German
    Type: reportzib , doc-type:preprint
    Format: application/pdf
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  • 2
    Publication Date: 2016-06-30
    Description: Executing applications in the Grid often requires access to multiple geographically distributed resources. In a Grid environment, these resources belong to different administrative domains, each employing its own scheduling policy. That is, at which time an activity (e.g., compute job, data transfer) is started, is decided by the resource's local management system. In such an environment, the coordinated execution of distributed applications requires guarantees on the quality of service (QoS) of the needed resources. Reserving resources in advance is an accepted means to obtain QoS guarantees from a single provider. The challenge, however, is to coordinate advance reservations of multiple resources. This work presents a system architecture and mechanisms to coordinate multiple advance reservations -- called co-reservations -- for delivering QoS guarantees to complex applications. We formally define the co-reservation problem as an optimization problem. The presented model supports three dimensions of freedom: the start time, the duration and the service level of a reservation. Requests and resources are described in a simple language. After matching the static properties and requirements of either side in a mapping, the reservation mechanism probes information about the future status of the resources. The versatile design of the probing step allows the efficient processing of requests, but also lets the resources express their preferences among the myriads of reservation candidates. Next, the best mapping is found through an implementation of the formal co-reservation model. Then, the mapping has to be secured, i.e., resources need to be allocated to a co-reservation candidate with all-or-nothing semantics. We study several goal-driven sequential and concurrent allocation mechanisms and define schemes for handling allocation failures. Finally, we introduce the concept of virtual resources for seamlessly embedding co-reservations into Grid resource management.
    Description: Die Ausführung von Anwendungen erfordert oft mehrere, geographisch verteilte Ressourcen. In Grid-Umgebungen gehören diese Ressourcen zu verschiedenen administrativen Organisationen, wobei jede ihre eigene Schedulingregeln verwendet. Das bedeutet, zu welcher Zeit eine Aktivität gestartet wird (z.B. ein Rechenjob), wird vom lokalen Ressourcenmanagementsystem entschieden. Die koordinierte Ausführung von verteilten Anwendungen erfordert Dienstgütegarantien für die benötigten Ressourcen. Das Reservieren von Ressourcen im Voraus ist ein Mittel, um Dienstgütegarantien von einem einzelnen Ressourcenanbieter zu erhalten. Die Herausforderung in dieser Arbeit ist, Vorausreservierungen von mehreren Ressourcen zu koordinieren. Es wird ein System für die Koordinierung mehrerer Vorausreservierungen -- Co-Reservierungen genannt -- für die Bereitstellung von Dienstgütegarantien vorgestellt. Wir definieren das Co-Reservierungsproblem als Optimierungsproblem. Das vorgestellte Modell unterstützt drei Freiheitsgrade: die Startzeit, die Dauer und die Dienstgüte einer Reservierung. Anfragen und Ressourcen werden in einer einfachen Sprache beschrieben. Nachdem statische Eigenschaften und Anforderungen beider Seiten überprüft wurden, ermittelt der Reservierungsmechanismus Informationen über den zukünftigen Zustand der Ressourcen. Dieser Schritt ist so allgemein gehalten, daß er sowohl ein effizientes Bearbeiten der Anfragen erlaubt als auch den Ressourcen ermöglicht ihre Präferenzen auszudrücken. Im Anschluss wird die optimale Zuweisung von Anfragen zu Ressourcen ermittelt. Im letzten Schritt muss diese Zuweisung umgesetzt werden, d.h., entweder alle oder keine Ressource wird allokiert. Es werden mehrere sequentielle und parallele Allokationsverfahren vorgestellt sowie deren Auswirkung auf verschiedene Metriken untersucht. Die Einbettung von Co-Reservierungen in das Grid-Ressourcenmanagement wird anhand des Konzeptes der virtuellen Ressource dargestellt.
    Keywords: ddc:004
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
    Format: application/pdf
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  • 3
    Publication Date: 2016-06-30
    Description: Aktuelle Entwicklungen zeigen, dass Peer-to-Peer (P2P) Anwendungen wie Skype oder Bittorrent im Internet immer mehr an Bedeutung gewinnen. In den letzten Jahren hat es einen explosionsartigen Anstieg an Nutzern und Daten in solchen Netzen gegeben. Dabei stellt der eigentliche Dateitransfer zwischen zwei Rechnern kein großes Problem mehr dar und auch der Speicherbedarf für die große Menge an Daten kann durch die Weiterentwicklung der Hardware gut gedeckt werden. Das eigentliche Problem liegt vielmehr darin, den Rechner zu finden, der die gewünschten Daten hat. Client-Server Architekturen, wie zum Beispiel Napster, haben sich als ungünstig herausgestellt. Wenige Server, die eine große Anzahl an Clients bedienen müssen, sind einerseits sehr anfällig gegenüber Angriffen und Ausfällen (Single Point of Failure)und kommen auch nicht mit der ständig wachsenden Anzahl an Nutzern zurecht. Verteilte Hashtabellen (DHT) bieten hier einen guten Lösungsansatz, der mit einer großen Anzahl an Nutzern skaliert und ausfallsicher ist. Andere dezentrale Lösungen, wie zum Beispiel das P2P Netzwerk Gnutella haben zwar das Problem des Single Point of Failure gelöst, jedoch haben sie starke Nachteile bei der Suche nach Keys. Bei einer Suche wird ein Broadcast verwendet (jeder schickt die Anfrage an jeden weiter) und damit ein enormer Netzwerkverkehr erzeugt. In "Why Gnutella Can't Scale. No, Really" wird erklärt, dass eine Suchanfrage bei Standardeinstellungen in der Clientsoftware einen Netzwerkverkehr von 17MB erzeugt. Deswegen wird zusätzlich eine Lösung benötigt, die Keys und Values geordnet verteilt, damit sie gezielt gesucht werden können. Aus diesem Grund beschäftigt sich die folgende Arbeit mit einer völlig dezentralen Architektur, die außerdem eine sinnvolle Platzierung der Keys vornimmt. Die dezentrale Architektur hat den Vorteil, dass die Endgeräte den Hauptteil des Dienstes selbst erbringen und damit jeder zusätzliche Teilnehmer seine eigenen Ressourcen beisteuert. Diese Arbeit präsentiert Chord#, eine dezentrale, skalierbare und selbstorganisierende verteilte Hashtabelle. Chord# wurde ausgewählt, da in dieser Arbeit auch Wert auf Bereichsabfragen gelegt wurde. Diese sind zum Beispiel bei dem Chord Algorithmus nicht möglich, da dieser eine Hashfunktion für die Keys verwendet und somit die Daten zwar gleichmäßig aber unsortiert auf die Teilnehmer verteilt. Es wird in dieser Arbeit gezeigt, dass mit Hilfe von Chord# auch ohne die Hashfunktion gute Ergebnisse erzielt werden. Außerdem können durch den Verzicht auf die Hashfunktion Bereichsabfragen ermöglicht werden. Dafür wird der Chord# Algorithmus in Java implementiert (ca. 1500 Zeilen Code) und in dem Forschungsnetz PlanetLab ausführlich auf Laufzeiten, Instandhaltungskosten und Skalierung getestet.
    Description: Recent developments show that peer-to-peer (p2p) applications, such as Skype or Bittorrent have become increasingly important in the internet. Over the last years there has been a rapid growth of both users and data in such networks. However, the actual file transfer between two peers is not really an issue anymore. The same holds true for data storage, since the new hardware grants users enough space to store their data. The real problem is finding the peers that possess the desired data. Client-server architectures like Napster have proven to be ineffective addressing that problem. One or few servers being responsible for many peers are vulnerable to attacks or failures (single point of failure). Additionally, they are unable to cope with the rapidly growing number of peers. Distributed hashtables (DHT) are a good approach to solve these problems, since they scale nicely with large numbers of peers and provide a high tolerance for errors. Other decentralized solutions like the p2p network Gnutella solved the problem of Single Point of Failure but show considerable disadvantages when searching for keys. The peers in Gnutella use a broadcast (sending the message to all peers they know)resulting in massive traffic. According to "Why Gnutella Can't Scale. No, Really.", each search using standard client settings yields 17MB traffc. This calls for a different solution, distributing keys and values to peers quickly and efficiently so they can be found fast. For that reason this thesis focuses on a fully distributed architecture using organized key placement. One major advantage of distributed architecture is the fact, that the peers do most of the work themselves. This way, new peers joining the network add resources to it. This thesis presents Chord#, a scalable, self-organizing and completely decentralized DHT. It has been chosen due to its capability to allow range queries. The regular Chord algorithm does not support range queries, because of the hashfunction it uses to evenly distribute the keys among the peers. This results in similar or logical coherent keys most likely not being close together in the network. This thesis shows Chord# achieving same results as Chord - regarding performance costs - without the hashfunction. In dropping the hashfunction this algorithm allows the use of range queries. The Chord# algorithm is implemented in Java (about 1500 lines of code) and thoroughly tested in the research network PlanetLab. The results are evaluated regarding performance, maintenance and scalability.
    Keywords: ddc:004
    Language: German
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 4
    Publication Date: 2017-11-02
    Description: One of the biggest impacts on the performance of a Distributed Hash Table (DHT), once established, is its ability to balance load among its nodes. DHTs supporting range queries for example suffer from a potentially huge skew in the distribution of their items since techniques such as consistent hashing can not be applied. Thus explicit load balancing schemes need to be deployed. Several such schemes have been developed and are part of recent research, most of them using only information locally available in order to scale to arbitrary systems. Gossiping techniques however allow the retrieval of fairly good estimates of global information with low overhead. Such information can then be added to existing load balancing algorithms that can use the additional knowledge to improve their performance. Within this thesis several schemes are developed that use global information like the average load and the standard deviation of the load among the nodes to primarily reduce the number of items an algorithm moves to achieve a certain balance. Two novel load balancing algorithms have then been equipped with implementations of those schemes and have been simulated on several scenarios. Most of these variants show better balance results and move far less items than the algorithms they are based on. The best of the developed algorithms achieves a 15-30% better balance and moves only about 50-70% of the number of items its underlying algorithm moves. This variation is also very robust to erroneous estimates and scales linearly with the system size and system load. Further experiments with self-tuning algorithms that set an algorithm’s parameter according to the system’s state show that even more improvements can be gained if additionally applied. Such a variant based on the algorithm described by Karger and Ruhl shows the same balance improvements of 15-30% as the variant above but reduces the number of item movements further to 40-65%.
    Keywords: ddc:004
    Language: English
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 5
    Publication Date: 2020-12-15
    Description: Entwurf und Entwicklung eines eingebetteten Hauptspeicher-Datenbanksystems mit Snapshot-Reads.
    Description: Design and implementation of an embedded main memory database with snapshot reads.
    Keywords: ddc:004
    Language: German
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 6
    Publication Date: 2016-06-30
    Description: Das Ziel dieser Arbeit ist die Schaffung einer Zugriffs-Komponente für das Grid-Datenmanagement-System ZIB-DMS, das dessen transparente Einbindung in den Verzeichnisbaum eines Linux-Systems erlaubt. Dazu wird unter Verwendung des FUSE-Rahmenwerkes ein Userspace-Dateisystem mit Anbindung an das ZIB-DMS konzipiert und implementiert. Im Fokus stehen dabei die Abbildung der erweiterten Verwaltungsmechanismen des Systems auf die limitierte Schnittstelle hierarchischer Dateisysteme und die dazu notwendigen Änderungen am ZIB-DMS.
    Description: The goal of this work is to create an access component for the Grid data management system ZIB-DMS, that allows a transparent integration into the directory tree of a Linux system. For this purpose the FUSE framework is used to design and implement a userspace file system with connections to the ZIB-DMS. The focus is on the mapping of the extended management mechanisms of the system to the limited interface of hierarchical file systems and the therefore necessary changes to ZIB-DMS.
    Keywords: ddc:004
    Language: German
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 7
    Publication Date: 2021-01-22
    Description: We present a framework for transactional data access on data stored in a DHT. It allows to atomically read and write items and to run distributed transactions consisting of a sequence of read and write operations on the items. Items are symmetrically replicated in order to achieve durability of data stored in the SON. To provide availability of items despite the unavailability of some replicas, operations on items are quorum-based. They make progress as long as a majority of replicas can be accessed. Our framework processes transactions optimistically with an atomic commit protocol that is based on Paxos atomic commit. We present algorithms for the whole framework with an event based notation. Additionally we discuss the problem of lookup inconsistencies and its implications on the one-copy serializability property of the transaction processing in our framework.
    Keywords: ddc:004
    Language: English
    Type: reportzib , doc-type:preprint
    Format: application/pdf
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  • 8
    Publication Date: 2020-12-11
    Description: When planning teams for projects with specific goals, employees of a company have to group together so well, that all necessary knowledge for conquering the project’s challenges are met within the member’s skills. A tool that facilitates semantic web technologies can support the team recruiter, who is responsible for chosing the members of the team, in terms of finding the most efficient combinations of the company’s employees based on their expertises.
    Keywords: ddc:004
    Language: English
    Type: reportzib , doc-type:preprint
    Format: application/pdf
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  • 9
    Publication Date: 2021-01-22
    Description: Key/value stores which are built on structured overlay networks often lack support for atomic transactions and strong data consistency among replicas. This is unfortunate, because consistency guarantees and transactions would allow a wide range of additional application domains to benefit from the inherent scalability and fault-tolerance of DHTs. The Scalaris key/value store supports strong data consistency and atomic transactions. It uses an enhanced Paxos Commit protocol with only four communication steps rather than six. This improvement was possible by exploiting information from the replica distribution in the DHT. Scalaris enables implementation of more reliable and scalable infrastructure for collaborative Web services that require strong consistency and atomic changes across multiple items.
    Keywords: ddc:004
    Language: English
    Type: reportzib , doc-type:preprint
    Format: application/pdf
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  • 10
    Publication Date: 2022-07-19
    Description: Basierend auf einem vorhandenen Ansatz zur Einführung von anisotropen Tetraedern im Randbereich eines reinen Tetraedergitters wird ein Gittergenerator für hybride Gitter implementiert. Das hybride Gitter besteht in Randnähe primär aus anisotropen Prismen und im Inneren der Geometrie aus isotropen Tetraedern. Eine erhöhte Auflösung im Randbereich soll zu besseren Ergebnissen von numerischen Strömungssimulationen führen, für welche eine problemangepasste Diskretisierung des zu untersuchenden Gebietes benötigt wird. In dem zuvor genannten Ansatz wird eine Reihe von Übergangselementen vorgeschlagen, die an scharfen Kanten der Oberfläche platziert werden sollen. Im Rahmen dieser Diplomarbeit wird die Idee der Übergangselemente aufgegriffen und bei hybriden Gittern eingesetzt, um auch komplexe Eingabegeometrien vergittern zu können. Der ursprüngliche Gittergenerierungprozess wird überarbeitet und erweitert. Eine neue Menge an Übergangselementen wird eingeführt, es werden gekrümmte Extrusionsvektoren verwendet und es wird die Auswertung der medialen Oberfläche vorgenommen, um Überschneidungen im hybriden Gitter zu vermeiden. Der Gittergenerator wird als Modul in das Visualisierungs- und Analyseprogramm Amira implementiert und die erstellten hybriden Gitter werden auf ihre Elementqualität und die Güte der Strömungssimulationsergebnisse hin überprüft.
    Description: Based on an existing approach for the introduction of anisotropic tetrahedra near the surface boundary of a tetrahedral grid a grid generator for hybrid grids is implemented. The hybrid grid consists near the surface boundary primarily of anisotropic prisms and inside the geometry of isotropic tetrahedra. An increased resolution near the boundary should lead to better results of numerical flow simulations, which needs a problem specific discretization of the analyzed domain. In the aforementioned approach a set of transition elements is suggested, which should be placed at sharp surface corners. As a part of this diploma thesis the concept of using transition elements is applied for creating hybrid grids even for very complex input geometries. The initial grid generation process is revised and enhanced. A new set of transition elements is introduced, curved extrusion vectors are used and the medial surface is evaluated to avoid intersections in the hybrid grid. The grid generator is implemented as a module for the visualization and analysis tool Amira and the element quality of the generated hybrid grids and the quality of flow simulations performed on the grids are tested.
    Keywords: ddc:004
    Language: German
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 11
    Publication Date: 2016-06-30
    Description: We study performance and scaling of the Berlin Quantum Chromodynamics Program (BQCD) on the SGI Altix 4700 at Leibniz Supercomputing Centre (LRZ). We employ different communication methods (MPI, MPI with two OpenMP threads per process, as well as the shmem library) and run the MPI version on the two types of nodes of that machine. For comparison with other machines we made performance measurements on an IBM p690 cluster and a Cray XT4.
    Keywords: ddc:004
    Language: English
    Type: reportzib , doc-type:preprint
    Format: application/pdf
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  • 12
    Publication Date: 2022-07-19
    Description: In dieser Arbeit wird eine Serie von Remeshing-Verfahren um die Berücksichtigung von nicht-mannigfaltigen Dreiecksvernetzungen und Merkmalskantenzügen erweitert. Die betrachteten Verfahren arbeiten im Wesentlichen lokal. Daher können die im Rahmen dieser Arbeit entwickelten Erweiterungen, die nicht-mannigfaltige Kantenzüge und Merkmalskantenzüge betreffen, separat beschrieben werden. Dabei wird ein Ansatz verfolgt, beide Arten von besonderen Kantenzügen aufgrund ihrer Gemeinsamkeiten einheitlich zu behandeln. Dieser besteht zum einen darin, eine Korrespondenz zwischen Kantenzügen auf der Eingabe- und der Ausgabefläche zu erhalten, indem die Remeshing-Operationen auf den Kantenzügen in entsprechend eingeschränkter Weise verwendet werden. Zum anderen wird beschrieben, wie die Abtastdichte der Kantenzüge dynamisch an die Abtastdichte der Umgebung angepasst werden kann, um für weitgehende Isotropie in der Nähe von Merkmalskantenzügen zu sorgen.
    Description: A unified approach for consistent remeshing of arbitrary non-manifold triangle meshes with additional user-defined feature lines is presented. The method is based on local operations only and produces meshes of high regularity and triangle quality while preserving the geometry as well as topology of the feature lines as well as the input mesh.
    Keywords: ddc:004
    Language: German
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 13
    Publication Date: 2022-07-19
    Description: This work introduces a novel streamline seeding technique based on dual streamlines that are orthogonal to the vector field, instead of tangential. The greedy algorithm presented here produces a net of orthogonal streamlines that is iteratively refined resulting in good domain coverage and a high degree of continuity and uniformity. The algorithm is easy to implement and efficient, and it naturally extends to curved surfaces.
    Description: In dieser Arbeit wird eine neue Strategie zur Platzierung von Stromlinien vorgestellt. Hierzu werden zusätzliche duale Stromlinien verwendet, die --im Gegensatz zur üblichen Definition-- orthogonal zum Vektorfeld verlaufen. Der vorgestellte Greedy-Algorithmus berechnet ein Netz aus orthogonalen Stromlinien, welches iterativ verfeinert wird, was zu einer guten Abdeckung der Domäne und einer gleichmäßigen Verteilung der Stromlinien führt. Es handelt sich um einen einfach zu implementierenden und effizienten Algorithmus, der direkt auf gekrümmten Oberflächen anwendbar ist.
    Keywords: ddc:004
    Language: English
    Type: reportzib , doc-type:preprint
    Format: application/pdf
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  • 14
    Publication Date: 2020-12-11
    Description: In dieser Diplomarbeit wird untersucht, wie auf der Basis von Literaturreferenzen ein Zitationsgraph durch ein automatisches Verfahren aufgebaut werden kann. Zur Lösung des Problems werden Probabilistische Relationale Modelle herangezogen. Eine problemspezifische Erweiterung des Modells ermöglicht es, dass bestehende Unsicherheiten im Zitationsgraphen mit Hilfe eines Inferenzverfahrens aufgelöst werden können. Zur Evaluierung des Verfahren werden Experimente auf dem Cora-Datensatz durchgeführt.
    Keywords: ddc:004
    Language: German
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 15
    Publication Date: 2016-06-30
    Description: Die Diplomarbeit präsentiert ein Transaktionsverfahren für strukturierte Overlay-Netzwerke, das an die Erfordernisse verteilter Informationssysteme mit relationalem Datenmodell angepasst ist. Insbesondere wird der Einsatz von Transaktionen für verteilte Wikis betrachtet, die moderne Funktionalitäten, wie Metadaten und zusätzliche Indexe für die Navigation, unterstützen. Konsistenz und Dauerhaftigkeit der gespeicherten Daten erfordert die Behandlung von Knotenausfällen. Die Arbeit schlägt dafür das Zellenmodell vor: Das Overlay wird aus replizierten Zustandsmaschinen gebildet, um Verfügbarkeit zu gewährleisten. Das Transaktionsverfahren baut darauf auf und verwendet Two-Phase-Commit mit Fehlererkennung und Widerherstellung von ausgefallenen Transaktionsmanagern. Anwendungen wird eine Auswahl an pessimistischen und hybrid-optimistischen Nebenläufigkeitskontrollverfahren geboten, die die Minimierung von Latenzeffekten und die schnelle Ausführung von Nur-Lese-Transaktionen ermöglichen. Für die Beispielanwendung Wiki wird der erforderliche Pseudocode angegeben und die verschiedenen Nebenläufigkeitskontrollverfahren hinsichtlich ihrer Nachrichtenkomplexität verglichen.
    Description: The diploma thesis presents a transaction processing scheme for structured overlay networks and uses it to develop a distributed Wiki application based on a relational data model. The Wiki supports rich metadata and additional indexes for navigation purposes. Ensuring consistency and durability requires handling of node failures. Such failures are masked by providing high availability of nodes. This in turn is achieved by constructing the overlay from replicated state machines (cell model). Atomicity is realized using two phase commit with additional support for failure detection and restoration of the transaction manager. The developed transaction processing scheme provides the application with a mixture of pessimistic, hybrid optimistic and multiversioning concurrency control techniques to minimize the impact of replication on latency and optimize for read operations. The pseudocode of the relevant Wiki functions is presented and the different concurrency control techniques are evaluated in terms of message complexity.
    Keywords: ddc:004
    Language: German
    Type: masterthesis , doc-type:masterThesis
    Format: application/pdf
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  • 16
    Publication Date: 2016-06-30
    Description: Die Arbeit präsentiert ein Transaktionsverfahren für strukturierte Overlay-Netzwerke, das an die Erfordernisse verteilter Informationssysteme mit relationalem Datenmodell angepasst ist. Insbesondere wird der Einsatz von Transaktionen für verteilte Wikis betrachtet, die moderne Funktionalitäten, wie Metadaten und zusätzliche Indexe für die Navigation, unterstützen. Konsistenz und Dauerhaftigkeit der gespeicherten Daten erfordert die Behandlung von Knotenausfällen. Die Arbeit schlägt dafür das Zellenmodell vor: Das Overlay wird aus replizierten Zustandsmaschinen gebildet, um Verfügbarkeit zu gewährleisten. Das Transaktionsverfahren baut darauf auf und verwendet Two-Phase-Commit mit Fehlererkennung und Widerherstellung von ausgefallenen Transaktionsmanagern. Anwendungen wird eine Auswahl an pessimistischen und hybrid-optimistischen Nebenläufigkeitskontrollverfahren geboten, die die Minimierung von Latenzeffekten und die schnelle Ausführung von Nur-Lese-Transaktionen ermöglichen. Für die Beispielanwendung Wiki wird der erforderliche Pseudocode angegeben und die verschiedenen Nebenläufigkeitskontrollverfahren hinsichtlich ihrer Nachrichtenkomplexität verglichen.
    Description: The report presents a transaction processing scheme for structured overlay networks and uses it to develop a distributed Wiki application based on a relational data model. The Wiki supports rich metadata and additional indexes for navigation purposes. Ensuring consistency and durability requires handling of node failures. Such failures are masked by providing high availability of nodes. This in turn is achieved by constructing the overlay from replicated state machines (cell model). Atomicity is realized using two phase commit with additional support for failure detection and restoration of the transaction manager. The developed transaction processing scheme provides the application with a mixture of pessimistic, hybrid optimistic and multiversioning concurrency control techniques to minimize the impact of replication on latency and optimize for read operations. The pseudocode of the relevant Wiki functions is presented and the different concurrency control techniques are evaluated in terms of message complexit
    Keywords: ddc:004
    Language: German
    Type: reportzib , doc-type:preprint
    Format: application/pdf
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  • 17
    Publication Date: 2016-06-30
    Description: Berlin als Stadtstaat ist Kommune und Land der Bundesrepublik zugleich und Standort vieler renommier-ter Wissenschafts- und Kultureinrichtungen. In enger Zusammenarbeit der Wissenschaftseinrichtungen mit dem IT-Dienstleistungszentrum Berlin (ITDZ, ehemals Landesbetrieb für Informationstechnik), der für die Behörden Berlins zuständigen Einrichtung, wurde seit 1993 ein landeseigenes Glasfasernetz mit einer derzeitigen Länge von 856 km Glasfaserkabel (je Kabel bis zu 144 Einzelfasern) zur gemeinsamen Nutzung von Wissenschaft und Verwaltung errichtet und weiter ausgebaut. 1994 erfolgte der offizielle Start des Berliner Wissenschaftsnetzes BRAIN (Berlin Research Area Information Network), als durch einen Beschluss des Senats von Berlin die Nutzung des landeseigenen Glasfasernetzes durch die Wissen-schaftseinrichtungen festgeschrieben wurde. Bereits 1995 wurden durch die Wissenschaftseinrichtungen auf diesem Glasfasernetz die ersten sieben Anschlüsse in ATM-Technik (Classical BRAIN-ATM) in Betrieb genommen, 1999 wurden anschließend auch erste Strecken in Ethernet-Technik (Classical BRAIN-GE) betrieben. Diese heterogenen Netze mit unterschiedlichen Netzgeräten wurden dezentral von den Netzadministratoren der beteiligten Einrichtungen nach globalen Absprachen betreut. Die dezentrale Administration erschwerte das Management und die Erweiterungen der Gesamtnetze. Basierend auf den vorliegenden Erfahrungen vereinbarten die Berliner Wissenschaftseinrichtungen, ein technisch neues Verbundnetz in Gigabit-Ethernet-Technik mit einheitlichen Geräten und einem zentralen Netzwerkmana-gement aufzubauen und zu betreiben. Seit November 2003 betreibt BRAIN auf dem landeseignen Glasfasernetz ein auf MPLS-Technik basie-rendes Gigabit-Ethernet-Netz, das „BRAIN-Verbundnetz“, mit den Diensten LAN-to-LAN-Kopplung der Einrichtungen, regionaler IP-Verkehr, Übergang zum Verwaltungsnetz und WiN-Backup. Das BRAIN-Verbundnetz löste die dezentral betreuten Vorläufernetze komplett ab. Von den derzeit 27 BRAIN-Teilnehmern nutzen 24 Einrichtungen an 53 in der Stadt verteilten Standorten die Dienste des BRAIN-Verbundnetzes, 18 Standorte sind mit 1000 Mbit/s und 35 Standorte mit 100 Mbit/s angeschlossen. Für verteilte Standorte einer Einrichtung besteht zudem die Möglichkeit, diese über dedizierte Fasern oder Bandbreiten miteinander zu vernetzen. Seit dem 2. Quartal 2007 wird im Rahmen eines Pilotprojekts der Nutzen eines zentral gemanagten Fibre Channel-Netzwerks "BRAIN-SAN" ermittelt, um Möglichkeiten einer verteilten Datenhaltung der Berliner Hochschulen und wissenschaftlichen Einrichtungen zu schaf-fen. Zusätzlich zu den vorgenannten Diensten nutzt der DFN-Verein die BRAIN-Struktur für die Verbindun-gen der X-WiN-Kernnetzknoten in Berlin und Potsdam untereinander und für Zugangsleitungen zu den Anwendern. Mit Stand 2007 nutzt das Berliner Wissenschaftsnetz BRAIN vom landeigenen Glasfasernetz 2100 km Einzelfasern und verbindet insgesamt 43 Einrichtungen (BRAIN-Teilnehmer und DFN-Anwender) aus Wissenschaft, Bildung und Kultur mit 129 Standorten. Der Betrieb von BRAIN wird im wesentlichen durch seine Nutzer finanziert. Das Land Berlin trägt aller-dings pauschal die überwiegenden Kosten für die Wartung des Glasfasernetzes, soweit es vom ITDZ be-reit gestellt wird. Zentrales Planungs- und Steuerungsorgan für BRAIN ist die von der Senatsverwaltung für Bildung, Wis-senschaft und Forschung eingerichtete BRAIN-Planungsgruppe. Sie besteht aus Mitarbeitern der Rechen-zentren der drei Berliner Universitäten und des ZIB. Nach außen wird BRAIN in rechtlicher und wirtschaftlicher Hinsicht treuhänderisch vom ZIB vertreten, die BRAIN-Geschäftsstelle befindet sich ebenfalls im ZIB.
    Description: Berlin as a city state is both local authority and federal state of the Federal Republic, as well as a location of many renowned institutions of research and culture. In close cooperation of the institutions of research with the IT service centre Berlin (ITDZ, the former Landesbetrieb für Informationstechnik) - which is the appropriate facility for the authorities of Berlin - a glass fibre network of a total extension of 856 kilome-tres of fibre optics (144 fibres each cable optic) for the common use of research and administration has been established and advanced since 1993. In 1994, when a resolution of the Senate of Berlin laid down the use of the appropriate fibre networks by the research facilities, this was the official beginning of the Berlin Research Area Information Network (BRAIN). The first seven interfaces in this fibre network in ATM technology (Classical BRAIN-ATM) were already established by the research facilities in 1995. In 1999, first systems run in Ethernet technology (Classical BRAIN-GE). These heterogeneous networks with different interfaces have been supported locally by the network administrators of the research facili-ties following global agreements. Management and advancement of the overall networks were encum-bered by these local administrations. Based on the existing experience, Berlin's research facilities agreed on the building and advancement of a technically new integrated network in gigabit Ethernet technology with standardised facilities and a centrally managed network. Since November 2003 the Berlin Research Area Information Network established a Gigabit Ethernet - called “BRAIN Integrated Network” - based on MPLS technology, including LAN to LAN linking of the facilities, local IP traffic, interface to the administration's network and WIN back-up. This BRAIN Inte-grated Network has completely replaced the locally administered predecessor networks. 24 of 27 BRAIN participants use the services of the BRAIN Integrated Network on 53 locations spread all over the city. 18 locations are connected with 1000 Mbit/s and 35 locations with 100 Mbit/s. Moreover, spread locations of a single facility have the possibililty to communicate by dedicated fibres or bandwidths. From the 2nd quarter 2007 within the scope of a pilot scheme, the advantage of a centrally administered fibre channel network "BRAIN-SAN" will be determined in order to accomplish possibilities of a spread data manage-ment of Berlin's universities and research facilities. In addition to the aforementioned services the DFN association makes use of BRAIN's structure for the connection of the X-WiN-core network nodes in Berlin and Potsdam und for access pathways to the us-ers. As from 2007, Berlin's research network BRAIN uses 2100 kilometres of single fibres from the country's fibre glass network and connects a total of 43 facilities (BRAIN participants and DFN users) from re-search, education and culture with 129 locations. The operations of BRAIN are funded basically by its users. However, the country of Berlin bears most of the costs for the maintenance of the glass fibre network, as far as it is provided by ITDZ. Central planning and steering body for BRAIN is the BRAIN planning group, which has been arranged by the administration of the Senatsverwaltung für Bildung, Wissenschaft und Forschung. It consists of staff from the computing centres of Berlin's three universities and of ZIB. BRAIN is represented legally and economically on a trust basis by the ZIB, where the BRAIN office is located also.
    Keywords: ddc:004
    Language: German
    Type: reportzib , doc-type:preprint
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  • 18
    Publication Date: 2022-07-19
    Description: For medical diagnosis, visualization, and model-based therapy planning three-dimensional geometric reconstructions of individual anatomical structures are often indispensable. Computer-assisted, model-based planning procedures typically cover specific modifications of “virtual anatomy” as well as numeric simulations of associated phenomena, like e.g. mechanical loads, fluid dynamics, or diffusion processes, in order to evaluate a potential therapeutic outcome. Since internal anatomical structures cannot be measured optically or mechanically in vivo, three-dimensional reconstruction of tomographic image data remains the method of choice. In this work the process chain of individual anatomy reconstruction is described which consists of segmentation of medical image data, geometrical reconstruction of all relevant tissue interfaces, up to the generation of geometric approximations (boundary surfaces and volumetric meshes) of three-dimensional anatomy being suited for finite element analysis. All results presented herein are generated with amira ® – a highly interactive software system for 3D data analysis, visualization and geometry reconstruction.
    Keywords: ddc:004
    Language: English
    Type: reportzib , doc-type:preprint
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  • 19
    Publication Date: 2022-07-19
    Description: This work introduces novel internal and external memory algorithms for computing voxel skeletons of massive voxel objects with complex network-like architecture and for converting these voxel skeletons to piecewise linear geometry, that is triangle meshes and piecewise straight lines. The presented techniques help to tackle the challenge of visualizing and analyzing 3d images of increasing size and complexity, which are becoming more and more important in, for example, biological and medical research. Section 2.3.1 contributes to the theoretical foundations of thinning algorithms with a discussion of homotopic thinning in the grid cell model. The grid cell model explicitly represents a cell complex built of faces, edges, and vertices shared between voxels. A characterization of pairs of cells to be deleted is much simpler than characterizations of simple voxels were before. The grid cell model resolves topologically unclear voxel configurations at junctions and locked voxel configurations causing, for example, interior voxels in sets of non-simple voxels. A general conclusion is that the grid cell model is superior to indecomposable voxels for algorithms that need detailed control of topology. Section 2.3.2 introduces a noise-insensitive measure based on the geodesic distance along the boundary to compute two-dimensional skeletons. The measure is able to retain thin object structures if they are geometrically important while ignoring noise on the object's boundary. This combination of properties is not known of other measures. The measure is also used to guide erosion in a thinning process from the boundary towards lines centered within plate-like structures. Geodesic distance based quantities seem to be well suited to robustly identify one- and two-dimensional skeletons. Chapter 6 applies the method to visualization of bone micro-architecture. Chapter 3 describes a novel geometry generation scheme for representing voxel skeletons, which retracts voxel skeletons to piecewise linear geometry per dual cube. The generated triangle meshes and graphs provide a link to geometry processing and efficient rendering of voxel skeletons. The scheme creates non-closed surfaces with boundaries, which contain fewer triangles than a representation of voxel skeletons using closed surfaces like small cubes or iso-surfaces. A conclusion is that thinking specifically about voxel skeleton configurations instead of generic voxel configurations helps to deal with the topological implications. The geometry generation is one foundation of the applications presented in Chapter 6. Chapter 5 presents a novel external memory algorithm for distance ordered homotopic thinning. The presented method extends known algorithms for computing chamfer distance transformations and thinning to execute I/O-efficiently when input is larger than the available main memory. The applied block-wise decomposition schemes are quite simple. Yet it was necessary to carefully analyze effects of block boundaries to devise globally correct external memory variants of known algorithms. In general, doing so is superior to naive block-wise processing ignoring boundary effects. Chapter 6 applies the algorithms in a novel method based on confocal microscopy for quantitative study of micro-vascular networks in the field of microcirculation.
    Description: Die vorliegende Arbeit führt I/O-effiziente Algorithmen und Standard-Algorithmen zur Berechnung von Voxel-Skeletten aus großen Voxel-Objekten mit komplexer, netzwerkartiger Struktur und zur Umwandlung solcher Voxel-Skelette in stückweise-lineare Geometrie ein. Die vorgestellten Techniken werden zur Visualisierung und Analyse komplexer drei-dimensionaler Bilddaten, beispielsweise aus Biologie und Medizin, eingesetzt. Abschnitt 2.3.1 leistet mit der Diskussion von topologischem Thinning im Grid-Cell-Modell einen Beitrag zu den theoretischen Grundlagen von Thinning-Algorithmen. Im Grid-Cell-Modell wird ein Voxel-Objekt als Zellkomplex dargestellt, der aus den Ecken, Kanten, Flächen und den eingeschlossenen Volumina der Voxel gebildet wird. Topologisch unklare Situationen an Verzweigungen und blockierte Voxel-Kombinationen werden aufgelöst. Die Charakterisierung von Zellpaaren, die im Thinning-Prozess entfernt werden dürfen, ist einfacher als bekannte Charakterisierungen von so genannten "Simple Voxels". Eine wesentliche Schlussfolgerung ist, dass das Grid-Cell-Modell atomaren Voxeln überlegen ist, wenn Algorithmen detaillierte Kontrolle über Topologie benötigen. Abschnitt 2.3.2 präsentiert ein rauschunempfindliches Maß, das den geodätischen Abstand entlang der Oberfläche verwendet, um zweidimensionale Skelette zu berechnen, welche dünne, aber geometrisch bedeutsame, Strukturen des Objekts rauschunempfindlich abbilden. Das Maß wird im weiteren mit Thinning kombiniert, um die Erosion von Voxeln auf Linien zuzusteuern, die zentriert in plattenförmigen Strukturen liegen. Maße, die auf dem geodätischen Abstand aufbauen, scheinen sehr geeignet zu sein, um ein- und zwei-dimensionale Skelette bei vorhandenem Rauschen zu identifizieren. Eine theoretische Begründung für diese Beobachtung steht noch aus. In Abschnitt 6 werden die diskutierten Methoden zur Visualisierung von Knochenfeinstruktur eingesetzt. Abschnitt 3 beschreibt eine Methode, um Voxel-Skelette durch kontrollierte Retraktion in eine stückweise-lineare geometrische Darstellung umzuwandeln, die als Eingabe für Geometrieverarbeitung und effizientes Rendering von Voxel-Skeletten dient. Es zeigt sich, dass eine detaillierte Betrachtung der topologischen Eigenschaften eines Voxel-Skeletts einer Betrachtung von allgemeinen Voxel-Konfigurationen für die Umwandlung zu einer geometrischen Darstellung überlegen ist. Die diskutierte Methode bildet die Grundlage für die Anwendungen, die in Abschnitt 6 diskutiert werden. Abschnitt 5 führt einen I/O-effizienten Algorithmus für Thinning ein. Die vorgestellte Methode erweitert bekannte Algorithmen zur Berechung von Chamfer-Distanztransformationen und Thinning so, dass diese effizient ausführbar sind, wenn die Eingabedaten den verfügbaren Hauptspeicher übersteigen. Der Einfluss der Blockgrenzen auf die Algorithmen wurde analysiert, um global korrekte Ergebnisse sicherzustellen. Eine detaillierte Analyse ist einer naiven Zerlegung, die die Einflüsse von Blockgrenzen vernachlässigt, überlegen. In Abschnitt 6 wird, aufbauend auf den I/O-effizienten Algorithmen, ein Verfahren zur quantitativen Analyse von Mikrogefäßnetzwerken diskutiert.
    Keywords: ddc:004
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 20
    Publication Date: 2022-07-19
    Description: One crucial step in virtual drug design is the identification of new lead structures with respect to a pharmacological target molecule. The search for new lead structures is often done with the help of a pharmacophore, which carries the essential structural as well as physico-chemical properties that a molecule needs to have in order to bind to the target molecule. In the absence of the target molecule, such a pharmacophore can be established by comparison of a set of active compounds. In order to identify their common features,a multiple alignment of all or most of the active compounds is necessary. Moreover, since the “outer shape” of the molecules plays a major role in the interaction between drug and target, an alignment algorithm aiming at the identification of common binding properties needs to consider the molecule’s “outer shape”, which can be approximated by the solvent excluded surface. In this thesis, we present a new approach to molecular surface alignment based on a discrete representation of shape as well as physico-chemical properties by points distributed on the solvent excluded surface. We propose a new method to distribute points regularly on a surface w.r.t. a smoothly varying point density given on that surface. Since the point distribution algorithm is not restricted to molecular surfaces, it might also be of interest for other applications. For the computation of pairwise surface alignments, we extend an existing point matching scheme to surface points, and we develop an efficient data structure speeding up the computation by a factor of three. Moreover, we present an approach to compute multiple alignments from pairwise alignments, which is able to handle a large number of surface points. All algorithms are evaluated on two sets of molecules: eight thermolysin inhibitors and seven HIV-1 protease inhibitors. Finally, we compare the results obtained from surface alignment with the results obtained by applying an atom alignment approach.
    Description: Die Identifizierung neuer Leitstrukturen (lead structures) zur Entwicklung optimierter Wirkstoffe ist ein äußerst wichtiger Schritt in der virtuellen Wirkstoffentwicklung (virtual drug design). Die Suche nach neuen Leitstrukturen wird oft mit Hilfe eines Pharmakophor-Modells durchgeführt, welches die wichtigsten strukturellen wie auch physiko-chemischen Eigenschaften eines bindenden Moleküls in sich vereint. Ist das Zielmolekül (target) nicht bekannt, kann das Pharmakophor-Modell mit Hilfe des Vergleiches aktiver Moleküle erstellt werden. Hier ist insbesondere die gleichzeitige Überlagerung (multiple alignment) aller oder nahezu aller Moleküle notwendig. Da bei der Interaktion zweier Moleküle die "äußere Form" der Moleküle eine besondere Rolle spielt, sollte diese von jedem Überlagerungsalgorithmus, der sich mit der Identifizierung von Bindungseigenschaften befasst, berücksichtigt werden. Dabei kann die "äußere Form" durch eine bestimmte Art von molekularer Oberfläche approximiert werden, die man als solvent excluded surface bezeichnet. In dieser Arbeit stellen wir einen neuen Ansatz zur Überlagerung molekularer Oberflächen dar, der auf einer diskreten Repräsentation sowohl der Form als auch der molekularen Eigenschaften mittels Punkten beruht. Um die Punkte auf der molekularen Oberfläche möglichst regulär entsprechend einer gegebenen Punktdichte zu verteilen, entwickeln wir eine neue Methode. Diese Methode ist nicht auf Moleküloberflächen beschränkt und könnte daher auch für andere Anwendungen von Interesse sein. Basierend auf einem bekannten Point-Matching Verfahren entwickeln wir einen Point-Matching Algorithmus für Oberflächenpunkte. Dazu erarbeiten wir u.a. eine effiziente Datenstruktur, die den Algorithmus um einen Faktor von drei beschleunigt. Darüberhinaus stellen wir einen Ansatz vor, der Mehrfachüberlagerungen (multiple alignments) aus paarweisen Überlagerungen berechnet. Die Herausforderung besteht hierbei vor allem in der großen Anzahl von Punkten, die berücksichtigt werden muss. Die vorgestellten Algorithmen werden an zwei Gruppen von Molekülen evaluiert, wobei die erste Gruppe aus acht Thermolysin Inhibitoren besteht, die zweite aus sieben HIV-1 Protease Inhibitoren. Darüberhinaus vergleichen wir die Ergebnisse der Oberflächenüberlagerung mit denen einer Atommittelpunktüberlagerung.
    Keywords: ddc:004
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 21
    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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  • 22
    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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  • 23
    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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  • 24
    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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  • 25
    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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  • 26
    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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  • 27
    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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  • 28
    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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  • 29
    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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  • 30
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1695-1702 
    ISSN: 1434-193X
    Keywords: Thiocarbonyl ylides ; Cycloadditions ; Dithiolanes ; Sulfur heterocycles ; Thioketones ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---2,5-Dihydro-2,2-diphenyl-1,3,4-thiadiazole (4) eliminates N2 at -45 °C and generates thiobenzophenone S-methylide (5), which is intercepted by dipolarophiles. The 1,3-cycloadditions of 5 with thiones (aromatic and aliphatic thioketones, dithioesters, trithiocarbonate) furnish 1,3-dithiolanes 7, in which the substituents, even voluminous ones, appear in the proximal 4- and 5-positions. The reaction of 5 with adamantanethione furnishes 7h and 4,4,5,5-tetraphenyl-1,3-dithiolane (7a) in a ratio of 4:1; a methylene transfer is involved, and the mechanistic pathways are discussed. The cycloadduct 7f originating from 5 and diphenyl trithiocarbonate undergoes an isomerization which consists of ionization and ring-opening leading to a ketene dithioacetal structure.
    Additional Material: 2 Ill.
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  • 31
    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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  • 32
    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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  • 33
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1905-1911 
    ISSN: 1434-193X
    Keywords: α,β-Epoxy ketones ; Rearrangements ; Zeolites ; Clays ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Various cyclic α,β-epoxy ketones rearranged to α-formyl ketones and/or vic-diones in the presence of catalytic amounts of zeolites and montmorillonite K10. This provides an excellent alternative to conventional homogeneous systems with respect to yields and workup. Differences in product distribution and type of products in the rearrangement of pulegone oxide could be reasonably explained by invoking different pathways for homogeneous and heterogeneous catalysts.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
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  • 34
    ISSN: 1434-193X
    Keywords: Amidines ; Chiral bases ; Enantioselective catalysis ; Enantioselective synthesis ; N-acyliminium ions ; Oxazaborolidines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The synthesis and X-ray crystal structures of three enantiopure hydroxy-substituted amidines of the DBN-type are described. The key starting material, a 5-(phenylsulfonyl)pyrrolidin-2-one, was obtained by an oxazaborolidine-catalysed reductive desymmetrization of a meso-imide and was functionalized through N-acyliminium ion chemistry. The hydroxy groups were introduced by ozonolysis or reduction. Preliminary results on the use of the hydroxyamidines as chiral, bifunctional catalysts in selected Michael reactions are described.
    Additional Material: 3 Ill.
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  • 35
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 199-204 
    ISSN: 1434-193X
    Keywords: Hexafluoroacetone ; N-Methylaspartic acid ; N-Methylglutamic acid ; N-Methyl-α-aminoadipic acid ; N-Methylthiazol-4-yl-α-amino acids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-Methylaspartic acid derivatives and its homologues are obtained by a stereoconservative one-pot procedure from hexafluoroacetone-protected aspartic and glutamic acid, 2a and 2b, respectively. α-Aminoadipic acid (5c) and its derivative 6c are accessible from the corresponding glutamic acid derivative 9b by a Wolff rearrangement. A variety of homochiral N-methylamino acids, 5 and 12, and their derivatives, 6 and 8-11, become readily available by the new synthetic concept.
    Type of Medium: Electronic Resource
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  • 36
    ISSN: 1434-193X
    Keywords: Fullerenes ; Cycloadditions ; Donor-acceptor systems ; Cyclic voltammetry ; Photoinduced electron transfer ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The new C60 and C70 adducts 1b, 1d-1k, 1m, 6d, 7d, and 8d have been synthesized by [2+3] cycloadditions of the appropriate nitrile oxides. Variations in the distance and geometry of the donor and acceptor substituents are seen to have an influence on the redox behavior of the fullerene adducts in cyclic voltammetry experiments. The isoxazolo-fullerenes 1c, 1d, and 1i show shifts of about 30 mV or 40 mV to more negative values compared with the reference compound 1a. On the other hand, strong acceptor properties are detected in the case of compound 1e, which shows a positive shift of 30 mV relative to 1a. Moreover, time-resolved fluorescence spectroscopy has shown that upon excitation of the fullerene moiety in the polar solvent benzonitrile, an electron is transferred from the donor substituent to the first excited singlet state of the fullerene, thereby reducing the excited-state lifetime. Our data demonstrate that the electron-transfer rate in donor-substituted fullerenes can be controlled by the electron-donating property of the substituent as well as the electronic structure and/or length of the spacer used. The C70 regioisomers 6d, 7d, and 8d exhibit differences in their spectroscopic characteristics.
    Additional Material: 3 Ill.
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  • 37
    ISSN: 1434-193X
    Keywords: Aminooxy group ; Phosphorylations ; Nucleotides ; Fluorescent labelling ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Preparation of the uridine and adenosine triphosphates 1 and 2 bearing a linker with a terminal aminooxy group is described. Both 1 and 2 react readily with the aldehydic fluorescein derivative 15. They could each be incorporated into a 330-mer fragment with T7 RNA polymerase.
    Additional Material: 2 Ill.
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  • 38
    ISSN: 1434-193X
    Keywords: “Proton sponge” analogues ; Orientation dependence of hydrogen bonds ; Crystal structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---1,2,4,5-Tetrakis(dimethylamino)benzene (4) and 2,3,6,7-tetrakis(dimethylamino)naphthalene (5) were prepared and structurally determined. Electron-donor functions, protonation, and the geometry of intramolecular hydrogen bonds are discussed. By oxidation of 4 to its dication the benzenoid aromaticity is cancelled in favour of two independent cyanine-type units as determined by X-ray structure analysis.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 39
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 365-380 
    ISSN: 1434-193X
    Keywords: Fluorescent dyes ; Perylenes ; Heterocycles ; NIR dyes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Core-extended perylenetetracarboxylic bisimides were prepared by Diels-Alder reaction followed by reduction, or by nitration followed by cyclisation. Highly fluorescent dyes were obtained with absorption regions from the visible to the NIR. Applications for solar energy harvesting, and quantum counters were suggested.
    Additional Material: 9 Ill.
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  • 40
    ISSN: 1434-193X
    Keywords: Radicals ; Photochemistry ; Aliphatic ethers ; Hydrogen abstraction ; Urazolyl radical ; α-Alkoxy-alkyl radical ; Diones ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The photoaddition of 4-methyl-1,2,4-triazoline-3,5-dione (4-MTAD) with a wide variety of acyclic, cyclic and crown aliphatic ethers has been investigated. Monochromatic (λ = 514.5 nm) or polychromatic (λ ≥ 310 nm) irradiations give identical mono-urazolyl ethers as reaction products. Unsymmetrical acyclic ethers afford a mixture of the two α and α′ mono-urazolyl ethers. In the case of 12-crown-4, mono and di-substituted products are obtained. ESR experiments and quantum calculations at the AM1 and 6-31G* levels were performed and a possible reaction mechanism is proposed in which the most probable photochemical process is the H-abstraction leading to a urazolyl radical.Supporting information for this article is available on the WWW under //http://www.wiley-vch.de/contents/jc_2046/2000/099269_s.pdf or from the author.
    Additional Material: 3 Ill.
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  • 41
    ISSN: 1434-193X
    Keywords: Photoinduced electron transfer ; Enantioselective syntheses ; Amino acids ; α-Hydroxy acids ; (S)-Prolinol ; Recyclable chiral auxiliary ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---PET activation of 1-(N-benzyl-N-methylglycyl)-(S)-prolinol (1) in dry acetonitrile, utilizing 1,4-dicyanonaphthalene (DCN) as a light-harvesting electron-acceptor and methyl viologen (MV++) as an electron-transfer mediator, leads to the formation of 3-[benzyl(methyl)amino]perhydropyrrolo[2,1-c][1,4]oxazin-4-one (3). When this photolysis is carried out in aqueous acetonitrile, exclusively 3-hydroxyperhydropyrrolo[2,1-c][1,4]oxazin-4-one (4) is produced. The formation of 3 can be rationalized in terms of intramolecular cyclization of the in situ generated iminium cation intermediate (2) by the OH moiety of (S)-prolinol, while 4 is generated by hydrolysis of 2 followed by acetalization. Nucleophilic alkylation of 3 and 4, using Grignard reagents and allyltrimethylsilane/TiCl4, provides 12a-d & 15 and 17a-c & 21, respectively, in a highly stereoselective manner. Hydrolysis of the resultant amides (12, 15, 17, and 21) provides α-amino acid derivatives (14) and α-hydroxy acids, respectively, in optically active form, along with the recovered (S)-prolinol chiral auxiliary in its recyclable form.
    Additional Material: 1 Ill.
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  • 42
    ISSN: 1434-193X
    Keywords: Tetrathiafulvalenes ; Charge transfer ; UV/Vis spectroscopy ; Cyclic voltammetry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---4-[2-tetrathiafulvalenyl-ethenyl]pyridine (1) has been prepared from a Wittig reaction between formyltetrathiafulvalene and 4-picolyltriphenylphosphonium chloride hydrochloride. Conversion of the pyridine moiety of 1 by reaction with methyl iodide leads to 4-[2-tetrathiafulvalenyl-ethenyl]-1-methylpyridinium iodide (2a). Neutralization of 1 with a large excess of L-tartaric acid affords 4-[2-tetrathiafulvalenyl-ethenyl]-1-methylpyridinium hydrogen tartrate (3). These TTF-π-spacer-acceptor compounds have been characterized by elemental analysis, and IR and 1H NMR spectroscopy. The crystal structure of 2a has been determined by X-ray diffraction. The cation is essentially planar. Examination of the bond lengths in 2a, UV/Vis spectra and CV data, and calculations indicate that an intramolecular charge transfer occurs in the studied compounds, although it is rather limited, and larger in 2a and 3 than in 1.
    Additional Material: 3 Ill.
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  • 43
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 807-811 
    ISSN: 1434-193X
    Keywords: Proline analogues ; Asymmetric synthesis ; Schöllkopf's method ; Silicon ; Amino acids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The asymmetric synthesis of a new proline surrogate, incorporating the dimethylsilyl group at position 4 of proline using Schöllkopf's bis-lactim ether method, is described.
    Type of Medium: Electronic Resource
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  • 44
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1345-1351 
    ISSN: 1434-193X
    Keywords: Kinetics ; Photochemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photochemical reaction of thionine (Th) with an organic reductant such as thioureas was studied in absolute methanol at constant temperature 25±0.1°C. Spectrophotometric methods were adopted for the determination of the values of absorbances in the presence of extremely dissociated, undissociated and partially dissociated acridine in absolute methanol. The acidity of the reaction solution H0 was controlled by using acetate buffer solutions. The effect of variables like concentration of thiourea, acidity and temperature on quantum yield (φ) was studied and the results were interpreted in terms of reaction mechanism. It was found that the quantum yield of the reactions of thionine with thiourea is controlled by two equilibria between (i) triplet state of thionine with proton and protonated triplet state of thionine, and (ii) protonated triplet state of thionine with reductant and associated complex (Th·H2T++·AH2).
    Additional Material: 5 Ill.
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  • 45
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1353-1357 
    ISSN: 1434-193X
    Keywords: Heterocycles ; Rearrangements ; C-C coupling ; C-C coupling ; Cyclizations ; Isoquinolines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -5-Methylbenzo[b]thieno[2,3-c]isoquinolines and 5-methylbenzo[b]seleno[2,3-c]isoquinolines 11b,c have been prepared by Bischler-Napieralski cyclization of 2-acetamido-3-phenylbenzo[b]heteroarenes.
    Additional Material: 4 Tab.
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  • 46
    ISSN: 1434-193X
    Keywords: Endoperoxides ; Cycloheptatriene ; Dichloroketene ; Singlet oxygen ; Cobalt ; Porphyrins ; Furans ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -CoII-tetraphenylporphyrin-catalyzed decomposition of bicyclic endoperoxides 4 and 5 with a strained double bond moiety has been studied. Compounds 4 and 5 have been synthesized by photooxygenation of 3 which itself was obtained by dichloroketene addition to cycloheptatriene, followed by removal of the chlorine atoms. An unusual decomposition mode of 4 promoted by CoII-TPP resulted in the formation of 8 and 9 which are important building blocks in furofuran systems.
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  • 47
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1373-1373 
    ISSN: 1434-193X
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -No Abstract.
    Type of Medium: Electronic Resource
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  • 48
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1365-1372 
    ISSN: 1434-193X
    Keywords: Atropisomerism ; Transition states ; Enzyme inhibitors ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Transition state mimicry is one of the most powerful concepts in enzyme inhibitor design and has led to the development of catalytic antibodies. Transition state analogs are compounds with a fixed shape that resemble the geometry and charge distribution of the transition state of a given reaction. Stabilization of a transition state like conformation is most often achieved by incorporating a ring system into the analog. We show herein that atropisomerism can be used as a new principle for enforcing a transition state like conformation. Atropisomerism relates to the existence of stereoisomers of structurally constrained molecules due to a frozen rotation about a single bond, as for example in binaphthol. The 1-aminomethylnaphthalene derivative 1 exhibits atropisomerism due to a frozen rotation about the C(1)-C(methylene) single bond, which holds the dihedral angle θ[C(2)-C(1)-C(methylene)-N] close to 90°. Compound 1 mimics the transition state for hydride transfer between 1,4-dihydroquinolines 4 and acetone.
    Additional Material: 5 Ill.
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  • 49
    ISSN: 1434-193X
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -No Abstract.
    Type of Medium: Electronic Resource
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  • 50
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1377-1386 
    ISSN: 1434-193X
    Keywords: Diallenes ; Solid-state reactions ; Naphthocyclobutenes ; Benzodicyclobutadiene ; Through-bond interactions ; X-ray analysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The title four-membered ring compounds, naphthocyclobutenes and benzodicyclobutadienes, were produced by thermal cyclization reaction of crystalline 1,2-diallenylbenzenes and 1,6-diethynyldiallenes, respectively. These solid-state reactions proceeded efficiently and stereoselectively. The naphthocyclobutenes were shown to have extremely long C(sp3)-C(sp3) bonds (1.720-1.733 Å). The benzodicyclobutadienes were also shown to have extremely long C(sp2)-C(sp2) bonds (1.540 Å).
    Additional Material: 4 Ill.
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  • 51
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1387-1389 
    ISSN: 1434-193X
    Keywords: Natural products ; Epoxidations ; Asymmetric synthesis ; Fluorine ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The synthesis of enantiomerically and diastereomerically pure (-)-(1R,2R,5R)- and (-)-(1R,2S,5R)-2-fluoro frontalin (7) starting from (+)-(1S)-menthyl-(R)-toluene-4-sulfinate, methylmagnesium bromide, methyl fluoroacetate, 4-pentenyl bromide and diazomethane is described. The absolute stereochemistry was unambiguously determined by X-ray analysis of (+)-(1S,2R,5S,RS)-5, an intermediate in the synthesis of the enantiomeric (+)-(1S,2R,5S)-2-fluoro frontalin (7).
    Additional Material: 2 Ill.
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  • 52
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 857-859 
    ISSN: 1434-193X
    Keywords: α,α-Dialkylated amino acids ; Isotopic labeling ; Strecker synthesis ; Solvent effects ; Stereoselective hydrolysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---[15N]-D-isovaline was prepared from DL-[α-15N]-α-aminoisovaleramide by enzymatic resolution with Mycobacterium neoaurum. The 15N-isotope was introduced during the Strecker synthesis of its precursor, e.g. aminoisovaleronitrile. Attempts to prepare the amino nitrile precursor of [15N]-α-aminoisobutyric acid (Aib) led to a poor yield and loss of the label. Significantly, improved results were obtained when a cosolvent is present during formation of aminoisobutyronitrile.
    Additional Material: 1 Ill.
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  • 53
    ISSN: 1434-193X
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No Abstract.
    Type of Medium: Electronic Resource
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  • 54
    ISSN: 1434-193X
    Keywords: Spiro compounds ; Ring-closing metathesis ; Pauson-Khand reaction ; Carbohydrates ; Enynes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The synthesis of the ketoglycosidic enynes 5, 7 and 8 starting from 2,3,4,6-tetra-O-benzyl-D-glucopyranolactone (2) is described. These enynes are subjected to ruthenium-mediated ring-closing metathesis and Pauson-Khand cyclisation to afford the highly functionalised carbohydrate spiroacetals 9 and 11-14.
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  • 55
    ISSN: 1434-193X
    Keywords: Asymmetric synthesis ; Nucleophilic formylation ; Addition reactions ; Lactones ; Formyl anion equivalent ; Domino reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---An efficient asymmetric synthesis of α-substituted β-formyl δ-lactones 5 (de ≥ 98%, ee = 80-95%) and 4-substituted furofuran lactones 6 (de ≥ 98%, ee = 80-〉98%) in acceptable overall yields is reported. Key steps of the new procedure are an asymmetric Michael addition of formaldehyde SAMP-hydrazone (1) to 5,6-dihydro-2H-pyran-2-one (2) under neutral conditions, followed by trans-selective α-alkylation and subsequent cleavage of the auxiliary by ozonolysis or a hydrolytic domino reaction protocol, respectively. The absolute configurations given for the title compounds are based on three X-ray structure analyses and NOE measurements.
    Additional Material: 3 Ill.
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  • 56
    ISSN: 1434-193X
    Keywords: Myxobacteria ; Antibiotics ; Cytotoxic ; Structure elucidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A novel highly cytotoxic metabolite, apicularen A (1), was isolated in a screening of the myxobacterial genus Chondromyces. The structure of 1 is characterized by a salicylic acid residue as part of a 10-membered lactone, which bears an acylenamine side chain. Compound 1 is an inhibitor of the proliferation of human cancer cell lines and induces apoptosis. Apicularen A (1) is present in nearly every strain of C. apiculatus, C. pediculatus, C. lanuginosus and C. robustus. Habitually 1 is accompanied by different amounts of a more polar variant, apicularen B (2), which was identified as 11-O-(2-N-acetamido-2-deoxy-β-D-glucopyranosyl)apicularen. According to feeding experiments with 13C-labeled acetates, glycine, and methionine, apicularen A (1) is an acetate-derived polyketide containing a glycine residue as precursor of the enamine. Uncommonly, the C3 starter unit is not assembled from propionate but from acetate and methionine.
    Additional Material: 6 Ill.
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  • 57
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1433-1441 
    ISSN: 1434-193X
    Keywords: Alkynes ; Annelation reactions ; Carbonyl compounds ; Heterocycles ; Polycycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Upon condensation of ortho-phenylenediamine (2) with ortho-alkynylbenzaldehydes in nitrobenzene, oxidative cyclizations are observed, which result in benzimidazo[2,1-a]isoquinolines (8) or isoindolo[2,1-a]quinoxalines (9) depending on the influence of additional substituents at the alkyne.
    Additional Material: 1 Ill.
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  • 58
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1443-1449 
    ISSN: 1434-193X
    Keywords: Amino acids ; Alkylations ; Phase-transfer catalysis ; Asymmetric synthesis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---N-(2-Nitrophenylsulfonyl)- (o-NBS-AA-OMe, 4) and N-(4-Nitrophenylsulfonyl)-α-amino acid methyl esters (p-NBS-AA-OMe, 5) were N-alkylated with a variety of alkyl halides 6 under solid-liquid phase-transfer catalysis (SL-PTC) conditions, affording the alkylated products o-NBS-N-R2-AA-OMe 7 and p-NBS-N-R2-AA-OMe 8 in excellent yields without any detectable racemization.
    Additional Material: 3 Tab.
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  • 59
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1451-1456 
    ISSN: 1434-193X
    Keywords: Mutolide ; Metabolites, secondary ; Macrolide ; Chemical screening ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The 14-membered macrolide, mutolide (1), was discovered by chemical screening of the culture broth of the fungus F-24′707y, obtained after UV mutagenesis of the wild type strain, which normally produces the spirobisnaphthalene cladospirone bisepoxide (2). The structure of 1 was established by detailed spectroscopic analysis, X-ray analysis and derivatisation. The biogenetic origin of the carbon skeleton and the hydroxy groups was verified by feeding sodium [1-13C]acetate and 18O2 to growing cultures of the fungus. Macrolide 1 is generated from acetate/malonate only. The unexpected change of the normal metabolite pattern of this strain is discussed, and proves the value of the OSMAC method.
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  • 60
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1457-1465 
    ISSN: 1434-193X
    Keywords: Sulfoximines ; Oxidative cleavage ; Sulfones ; Polymer-bound sulfoximines ; Solid-phase synthesis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Reaction of N-alkyl, N-aryl, and N-H sulfoximines with m-chloroperbenzoic acid cleanly gives the corresponding sulfones in high yield. In the case of the cleavage of N-alkyl and N-arylsulfoximines, formation of the corresponding nitroso compounds as the other reaction product was proven. Starting from enantio- and diastereopure sulfoximines, a number of chiral sulfones, including the axially chiral sulfone 6 and the sulfonyl-functionalized homoallylic alcohol 8, have been prepared. Reaction of the enantiopure sulfoximine 30 with Merrifield resin gave the polymer-bound sulfoximine 32. Oxidative cleavage of 32 afforded the sulfone 16 in high yield. Deprotonation of the sulfoximine resin 32 and reaction of Li-32 with benzaldehyde and propanal furnished the β-hydroxysulfoximine resins 33a and 33b, respectively. Oxidative cleavage of 33a and 33b readily afforded the β-hydroxy sulfones 14a and 14b, respectively.
    Additional Material: 1 Ill.
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  • 61
    ISSN: 1434-193X
    Keywords: Glycosyl phosphates ; Nucleosidephosphate sugars ; Neuraminic acid ; Glycosyltransferase ; Carbohydrates ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The reaction of sialyl phosphites 1, 22a-d, 28, 39, and 45 with acyl-protected riboside 5-phosphorous acids 2a,b and 23 directly furnished, without addition of a catalyst, under phosphite/phosphate exchange the corresponding β-configured sialyl riboside monophosphates 3a,b, 24a-d, 29, 46, and 47. The synthesis of the starting materials, formation of the products, and their treatment with sodium methanolate in methanol and subsequent hydrolysis of the sialic acid ester moiety to provide the unprotected target molecules 4a,b, 25a-d, 30, 48, and 49 is described. Investigations with α(2-6)-sialyltransferase from rat liver showed that base replacement in CMP-Neu5Ac (4a,b) is not tolerated by the enzyme but that modifications of the 5-, 8-, or 9-position of the neuraminic acid residue (25a-d, 30, 48, 49) are tolerated.
    Additional Material: 1 Tab.
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  • 62
    ISSN: 1434-193X
    Keywords: Titanium ; Acetals ; Cyclizations ; Synthetic methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---η3-Crotyltitanocenes react with acetals to produce homoallylic ethers. The intramolecular coupling involving tethered dienyl acetals provides a convenient access to vinylcycloalkanes and bicyclic fused compounds. This new cyclization reaction proceeds with a total regioselectivity in the exo fashion, and with good to excellent diastereoselectivity depending especially on the tether chain length.
    Additional Material: 3 Tab.
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  • 63
    ISSN: 1434-193X
    Keywords: Ene reactions ; Azepines ; Aminoacroleins ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The reaction of 3-[N-(alk-2-enyl)benzylamino]-2-cyanoacroleins 9 with primary amines 12 and 13 gave 4,5-dihydro-1H-azepines 14 and 15 stereoselectively, through an intramolecular ene reaction of the imine derivatives of 9. Similarly, carbonyl-ene reaction of acrolein derivatives 9, and olefin-ene reaction of their conjugated diene compounds 22, and 24-27 are also discussed. These ene reactions established an efficient synthetic approach toward monocyclic azepine ring formation.
    Additional Material: 1 Ill.
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  • 64
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1503-1505 
    ISSN: 1434-193X
    Keywords: Lactams ; Reductions ; Boranes ; Nitrogen heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Lactams containing an N-H bond are smoothly transformed into 2,2-diallylated nitrogen heterocycles on heating with allylic boranes in THF followed by deboronation
    Additional Material: 1 Tab.
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  • 65
    ISSN: 1434-193X
    Keywords: Asymmetric synthesis ; Phosphazene base ; Pyridyl epoxide ; Furyl epoxide ; Pyridyl alcohol ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---trans-1-(2-Pyridyl)-, trans-1-(3-pyridyl)-, trans-1(2-furyl)-, and trans-1(3-furyl)-2-phenyl epoxides with enantiomeric purities ranging from 96.8 to 99.8% [in favor of the (+, EtOH)-isomer] are obtained in two steps from pure (R,R,R)-oxathiane which is recovered (85-90%) and reused. The chiral bidentate ligand 2-phenyl-(S)-1-(2-pyridyl)ethanol with 99.6% ee was obtained in three steps and 67% overall isolated yield.
    Additional Material: 1 Ill.
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  • 66
    ISSN: 1434-193X
    Keywords: Cyclodextrins ; Inclusion compounds ; Carcinine ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A new modified β-cyclodextrin (β-CD) derivative 1 that was functionalized in position 6 with Boc-Carcinine was synthesised and its crystal structure was determined. The structure reveals a “sleeping swan”-like shape, the covalently bonded Boc-Carcinine moiety forming a folded structure with the Boc group inserted within the hydrophobic cavity of the β-cyclodextrin. The conformation of the Carcinine moiety is determined by the inclusion of the Boc group and is further stabilised by three intramolecular hydrogen bonds, two between the amide N1-H group, the carbonyl C′1=O1 group and a primary hydroxylic group of the glucose unit 5, one between the carbonyl C′0=O0 group and the primary hydroxylic group of the glucose unit 2. The β-CD macrocycle differs only slightly from unmodified β-CDs, maintaining an approximate sevenfold symmetry. The solution structure of the new β-CD derivative was investigated by NMR spectroscopy and circular dichroism (c.d.) spectroscopy. In addition to a complete (1H and 13C) assignment of the pendant Boc-Carcinine group, the NMR study allowed the assignment of all the proton resonances associated with the β-CD macrocycle. Furthermore, NMR and c.d. results indicated that the self-inclusion of the Boc group within the β-CD cavity is retained in aqueous solution. In order to estimate the strength of this self-inclusion complex a series of competition experiments with the external guest 1-adamantanol was carried out using c.d. spectroscopy.
    Additional Material: 9 Ill.
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  • 67
    ISSN: 1434-193X
    Keywords: Photochemistry ; Radicals ; EPR spectroscopy ; Quantum mechanical calculations ; Silicon compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Trisilane 7 has been synthesized as a potential photochemical precursor of tetra-tert-butylsilatetrahedrane (5) and/or tetra-tert-butylsilacyclobutadiene (6). Astonishingly, only one Si,Si bond is broken upon irradiation of 7 and the silacyclobutenyl radical 9 can be identified as the reaction product. The structure of radical 9, which in the absence of oxygen is persistent even at room temperature, has been elucidated by comparison of its experimental and calculated ESR spectra.
    Additional Material: 2 Ill.
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  • 68
    ISSN: 1434-193X
    Keywords: Catalytic hydrogenation ; Ruthenium complexes ; Sulfoxides ; Sulfoxides ; Asymmetric induction ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The diastereoselective catalytic hydrogenation of β-keto sulfoxides in the presence of ruthenium complexes was studied. Optically pure β-keto sulfoxides were hydrogenated in the presence of achiral catalysts leading to moderate yields and stereoselectivities. Using chiral ruthenium catalysts such as [(R)-MeO-BIPHEPRuBr2] and [(S)-MeO-BIPHEPRuBr2], the hydrogenation proceeded in good yields with very high diastereoselectivity. Chirality at the secondary centre of the β-hydroxy sulfoxides produced was controlled by the catalysts.
    Additional Material: 2 Ill.
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  • 69
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    Liebigs Annalen 2000 (2000), S. 1157-1163 
    ISSN: 1434-193X
    Keywords: Supramolecular chemistry ; Fullerenes ; Crown compounds ; Electrochemistry ; Metal complexation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The synthesis of two novel [60]fullerene derivatives containing the electron donor tetrathiafulvalene and metal-complexing crown ethers is described, and their complexation ability with alkali metal cations is studied by solid-liquid extraction techniques, cyclic voltammetry and 1H NMR spectroscopy.
    Additional Material: 4 Ill.
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  • 70
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    Liebigs Annalen 2000 (2000), S. 1165-1171 
    ISSN: 1434-193X
    Keywords: Porphyrinoids ; Asymmetric catalysis ; Atropisomerism ; Epoxidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -A new series of porphyrins has been synthesised, incorporating four identical chiral binaphthyl derivatives in the meso-positions. Owing to a hindered rotation around the bond between the naphthyl and the porphyrin, four atropisomers are generated, which were fully separated by preparative TLC and thoroughly characterised. The free bases were metallated with iron(III) and manganese(III) and the resulting complexes were used as catalytic precursors in styrene epoxidation. The reactions show chemoselectivity and enantioselectivity, depending on the stereochemistry of the metalloporphyrin. It is demonstrated that highest efficiency is performed by the ααββ isomer, showing C2 symmetry.
    Additional Material: 4 Ill.
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  • 71
    ISSN: 1434-193X
    Keywords: Carbene complexes ; 1-Metallahexatrienes ; Cyclopentadienes ; Carbene complexes ; Tungsten ; Domino cyclization ; Pentalenes ; Spirocyclopentanes ; Spiro compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -1,3-Dioxytetrahydropentalenes 9 have been generated by base-catalyzed addition of protic oxygen nucleophiles ROH 6a-g (RO = carboxy or phenyloxy) to the [2-(1-cyclopentenyl)ethynyl]carbene tungsten complex 3. Compounds 9 are highly reactive and afford (cyclobutenyl)carbene complexes 12a-g through spontaneous [2+2] cycloaddition to a second molecule of the (1-alkynyl)carbene complex 3. Thermolysis of compounds 12 was found to generate indeno[b]-spiro-tricyclo[5.3.0.0]decadienes 18 through π-cyclization of the 1-tungsta-1,3,5-hexatriene unit involving insertion of carbon monoxide into the W—C bond.
    Additional Material: 3 Ill.
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  • 72
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    Liebigs Annalen 2000 (2000), S. 1193-1197 
    ISSN: 1434-193X
    Keywords: Porphyrinoids ; Light-harvesting structures ; Energy transfer ; Nanostructures ; Photochemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The synthesis of niphaphyrins, a new class of rigid, snowflake-shaped porphyrin hexamers designed to mimic the light-harvesting antenna complexes of photosynthetic purple bacteria, is described. In these D6- or D3-symmetric assemblies, six porphyrin macrocycles, as free bases or as zinc chelates, are covalently attached to the six positions of a benzene core through rigid ethynyl linkers. A very efficient singlet excited-state energy transfer has been observed from the Zn chelates to the free-base porphyrin (Fb) chromophores in a niphaphyrin in which three zinc porphyrin chelates alternate with three porphyrin free bases. The overall yield of energy transfer (ΦET) has been estimated as 98%.
    Additional Material: 2 Ill.
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  • 73
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    Liebigs Annalen 2000 (2000), S. 1219-1228 
    ISSN: 1434-193X
    Keywords: Peptidomimetics ; Peptidosulfonamides ; Peptidomimetics ; Transition-state isosteres ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -In this paper we present a synthesis of both α- and β-substituted aminoethane sulfonamide arginine mimics. The α-substituted sulfonamides were obtained starting from an alkene, whereas the β-substituted sulfonamides were derived from an amino acid derivative.
    Additional Material: 1 Ill.
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  • 74
    ISSN: 1434-193X
    Keywords: Nucleophilic additions ; Nucleophilic substitutions ; Azabutadienes ; Δ2-Oxazoline ; Azabutenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The reaction of some sodium alkoxides with 4,4-dichloro-1,1-diphenyl-2-azabuta-1,3-diene is described. Whereas sodium methoxide, ethoxide or isopropoxide leads to 1,3-bis(alkoxy)- and/or 1,3,4-tris(alkoxy)-2-azabut-2-enes, the sodium salt of ethyl glycolate gives a Δ2-oxazoline. Mechanisms for the formation of these products are proposed.
    Additional Material: 3 Ill.
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  • 75
    ISSN: 1434-193X
    Keywords: Azides ; Cleavage reactions ; Cycloadditions ; Nitrogen heterocycles ; Ring expansion ; Sulfur heterocycles ; Synthetic methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Deprotonation of the 2-cycloalkylbenzothiazolium perchlorates 1f-h with sodium hydride in the presence of methanesulfonyl azide (3) affords the spirocyclic dihydro-1,4-benzothiazines 9f-h together with small amounts of the 2-iminobenzothiazole 5. The 2-cycloalkylidenedihydrobenzimidazoles 11e-h are generated by deprotonation with potassium hydride from the corresponding 2-cycloalkylbenzimidazolium salts 10e-h, and trapped with 3 to yield the zwitterions 12e-h. Whereas 12h is thermally unstable, 12e-g are isolated and thermolysed at 20-80 °C. The cyclopropyl zwitterion 12e decomposes in an ill-defined way, only at temperatures above 80 °C. In contrast, 12f,g, and, in particular, 12h, decompose more readily to furnish the products of ring expansion (13f-h) and those of a [3 + 2] cycloreversion (6 and 14) of intermediate spirocyclic triazolines. Products that might be indicative of the intervention of hypothetical zwitterions of type 8 cannot be detected.
    Additional Material: 4 Tab.
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  • 76
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    Liebigs Annalen 2000 (2000), S. 1241-1251 
    ISSN: 1434-193X
    Keywords: Amino acids ; Enolates ; Rearrangements ; Metal complexes ; Peptides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Deprotonation of allylic esters of peptides at -70 °C in the presence of metal salts results in the formation of metal peptide enolate complexes, which undergo Claisen rearrangement on warming to room temperature to produce stereoselectively modified peptides. By far the best results are obtained with manganese enolates. With these enolates, the amino acids incorporated in the peptide chain have no significant influence on the rearrangement, neither on the yield nor on the stereochemical outcome. Therefore, this protocol is extremely suitable for the stereoselective modification of peptides by using esters of chiral allylic alcohols. α-Alkylated amino acids can be incorporated into peptides as well.
    Additional Material: 2 Tab.
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  • 77
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 13-16 
    ISSN: 1434-1948
    Keywords: Pyrazole ; Titanium ; Redox reaction ; Mercury ; Amalgams ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reduction of [L2TiCl2] (1) (L = 3,5-tert-butylpyrazolate) with 1% Na/Hg in tetrahydrofuran (THF) affords the complex [L2TiCl(THF)2] (2), which crystallizes from hexane in moderate yield. The analogous reduction carried out in toluene gives dimeric [(L2TiCl)2] (3) in high yield. If the reduction time is extended to 3 days, the complex [L3Ti] (4) is isolated as light blue crystals in low yield. An alternative procedure for preparing compound 4 requires mixing [TiCl3(THF)3] with 3 equivalents of potassium 3,5-tert-butylpyrazolate in toluene. Crystallization from hexane affords 4 in high yield. Crystallographic data for 2, 3 and 4 are presented.
    Additional Material: 3 Ill.
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  • 78
    ISSN: 1434-1948
    Keywords: Polyoxometalates ; Ruthenium ; Homogeneous catalysis ; Oxidations ; Microwaves ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Microwave irradiation for 15 minutes allowed the highly selective hydrothermal synthesis of the diamagnetic, air-stable oxidation catalyst [PW11O39RuII(DMSO)]5-, as confirmed by 1H, 31P, 99Ru and 183W NMR techniques.
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  • 79
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 29-32 
    ISSN: 1434-1948
    Keywords: Arene complexes ; Ruthenium ; Benzimidazole ; Benzothiazole ; Benzoxazole ; Cycloisomerisation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fourteen ruthenium(II) complexes of the type [RuCl2(η6-arene)L], (arene = 1,4-MeC6H4Pri or C6Me6; L = benzimidazole derivative in which the NH group is substituted by N-alkyl or isoelectronic O or S atoms) have been prepared by cleavage of [RuCl2(η6-arene)]2 with the N-heterocycle L. Their spectroscopic and electrochemical properties are described. The effect of the nature of the benzazole (L) on the catalytic activity of these complexes for the intramolecular cyclization of (Z)-3-methylpent-2-en-4-yn-1-ol into 2,3-dimethylfuran has also been studied; the benzimidazole complexes were found to be the most active.
    Additional Material: 5 Tab.
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  • 80
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 59-63 
    ISSN: 1434-1948
    Keywords: Phosphorane imine ; Sulfur ligands ; Nickel ; Palladium ; Platinum ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of the trinuclear [M(′S3′)]3 complexes {M = Ni (4), Pd (5), Pt (6); ′S3′2- = bis(2-mercaptophenyl)sulfide (2-)} with HNPnPr3 yielded the new phosphorane imine complexes [M(NHPnPr3)(′S3′)] {M = Ni (1), Pd (2), Pt (3)}. The complexes 1-3 have been completely characterized and are rare examples of mononuclear phosphorane imine complexes with late transition metals. Spectroscopic and structural results indicate that the HNPnPr3 ligands favor the ylidic structure when binding to [M(′S3′)] fragments. X-ray structure determinations showed that [M(NHPnPr3)(′S3′)] complexes associate through N-H···S(thiolate) bridges to give centrosymmetric dimers.
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  • 81
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 75-82 
    ISSN: 1434-1948
    Keywords: Macrocyclic ligands ; Conformational equilibria ; EXSY spectroscopy ; Lanthanide-induced shifts ; Solution structure ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure and the conformational equilibria in aqueous and methanolic solutions of YbDOTMA (DOTMA = (1R,4R,7R,10R)-α,α′,α′′,α′′′′-tetramethyl-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) are investigated and the dynamics studied by means of NMR methods. The presence of two isomeric forms in slow exchange is confirmed and quantitatively characterized by EXSY. The exchange peaks are assigned to the inversion of the conformation of the macrocycle ring. No evidence is obtained of a reorientation of the methyl acetate substituents. The protons switch between positions with the same geometrical factors, i.e. positions that would have the same pseudocontact shifts were it not for the different magnetic susceptibility anisotropies of the two species; steady-state NOE spectra on the major form allow unequivocal assignment of the conformations of the two isomers.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99141_s.pdf or from the author.
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  • 82
    ISSN: 1434-1948
    Keywords: Photocatalysis ; Polyoxotungstates ; Catalytic oxidations ; Iron porphyrins ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photoexcitation of (nBu4N)4W10O32 is a suitable mean of oxidizing cyclohexene and cyclooctene with O2 at room temperature and pressure. This process can be carried out in homogeneous solution as well as using the decatungstate in a dispersed form after its heterogenisation on silica. Cyclohexene and cyclooctene are mainly oxidized to the corresponding hydroperoxides as a consequence of primary photoprocesses which lead to the formation of allylic radicals. The presence of the FeIII[meso-tetrakis(2,6-dichlorophenyl)porphyrin] chloride as cocatalyst strongly affects the photocatalytic properties of (nBu4N)4W10O32, playing a key role in the allylic-hydroperoxide dependent oxidation of the cycloalkenes. In the photooxidation of cyclohexene, the porphyrin increases the photocatalytic efficiency of the decatungstate in terms of total turnover number and catalyses the decomposition of cyclohexenyl hydroperoxide with the selective formation of cyclohex-2-en-1-ol. On the other hand, its presence during the photoinduced oxidation of cyclooctene favours the formation of cyclooctene epoxide by addition of ROO· and RO· radicals to the double bond. In the case of cyclooctene, the heterogenisation of the decatungstate on the solid support also affects the chemoselectivity of the photocatalytic process in the absence of the iron porphyrin complex.
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  • 83
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 103-112 
    ISSN: 1434-1948
    Keywords: Ab initio calculations ; Ionization potentials ; Phosphorus ; Heterocycles ; Small ring systems ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ab initio quantum chemical calculations have been used to explore the P3H3 potential energy surface focussing on the ring-chain rearrangements of the three-membered ring in (PH)3 (1), the parent triphosphirane. Relative energies between stationary points were estimated using the QCISD(T)/6-311G(d,p) method based on MP2/6-31G(d,p) geometries and corrected for zero-point contributions. Ring strain, proton affinities, ionization and excitation energies and heats of formation have been evaluated using larger basis sets, e.g. 6-311++G(3df,2p). The cyclic trans-triphosphirane (1a) is the most stable P3H3 isomer and lies about 40 kJ/mol below the open-chain phosphanyldi-phosphene (H2P-P=PH). The decrease of ring strain in three-membered rings when CH2 is replaced by PH is confirmed. Triphosphirane 1a is a virtually strain-free ring and even gains some stabilization relative to three separate P-P single bonds. The reduced ring strain also helps diminish the phosphorus inversion barrier to 224 kJ/mol compared to the monocyclic isomers of (CH2)(PH)2 and (CH2)2(PH). Compound 1a follows a pure ring-opening or a 1,2-hydrogen shift rather than a combined motion pathway, in fundamental contrast with corresponding processes of diphosphirane and phosphirane. This is due to the existence of an open-chain P3H3 phosphorane intermediate stabilized by allylic conjugation. The pericyclic ring-opening of 1a is the most favored process but the energy barrier in the gas phase is about 180 kJ/mol high. Electron density is largely delocalized within the three-membered P3 ring not only in the C3v-symmetric 1b (all-cis) but also in 1a (Cs). The proton affinity of 1a is similar to that of PH3. The proton affinities decrease with n in cyclo-(CH3)3 -n(PH)n and their values were obtained: PA(1a) = 777 ±10, PA(diphosphirane) = 799 ±10 and PA(phosphirane) = 802 ±10 kJ/mol. Heats of formation are evaluated as follows (ΔH°f0 at 0 K in kJ/mol): 1a, 70 ±10; cyclo-(PH)2(PH2)+ (protonated 1a), 821 ±10; diphosphirane, 85 ±10; cyclo-(CH2)(PH)(PH2)+ (protonated diphosphirane), 814 ±10; phosphirane, 86 ±10; and protonated phosphirane, 812 ±10 kJ/mol. All P rings remain cyclic following ionization to the radical cations. Adiabatic ionization energies (IEa) are estimated as: 1a and diphosphirane, 9.3 ±0.3 eV and phosphirane 9.5 ±0.3 eV. The first UV absorption band shifts toward the longer wavelength region on going from phosphirane to 1a. The GIAO/B3LYP computed magnetic shieldings for 1a and related molecules reveal a clear relationship between the narrow bond angles in the rings and their unusually strong magnetic shielding. The similarity of the predicted 31P-NMR signals in 1a and its heteroanalog diphosphirane, (CH2)(PH)2, can be rationalized in terms of a compensation of the carbon-substituent effect (downfield shift) and the bond-bending effect imposed by the ring (upfield shift).
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  • 84
    ISSN: 1434-1948
    Keywords: Thiolato-bridged complexes ; Iron ; Ruthenium ; Mixed-valent compounds ; Mössbauer spectroscopy ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of [FeIIIL] with [RuIICl2(dmso)4] in methanol under argon, affords, upon addition of NaPF6, brown crystals of [LFeRuFeL](PF6)2· 3 CH3OH (1). Its one-electron oxidation product [LFeRuFeL](PF6)3 (2) [L = 1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane] was generated by using one equivalent of [NO]BF4. The crystal structure determination of [LFeRuFeL](BPh4)2· CH3CN · 3 (CH3)2CO shows that 1 contains a trinuclear, face-sharing thiolato-bridged dication. Mössbauer spectroscopy established that the oxidation state distribution of 1 can best be described by Fe2.5RuIIIFe2.5 and 2 by FeIIIRuIIIFeIII. Complex 1 possesses a diamagnetic (St = 0) and 2 an St = 1/2 ground state. The electronic structures of 1 and 2 are rationalized by an MO picture involving Fe-Ru metal-metal bonds of bond order 0.5 in both species. Complex 1 is formally a mixed valence compound with complete delocalization of the “excess electron” (class III).
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  • 85
    ISSN: 1434-1948
    Keywords: Platinum ; Uracil ; Nucleobase ; Host-guest chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The open “molecular box” [(en)Pt(U-N1,N3)]4 (1) (where en = ethylenediamine, U = uracil dianion) is able to act as an efficient ligand for additional metal ions. Reactions of the 1,3-alternate conformer of 1 with divalent metal ions result in the formation of octanuclear compounds of the general formula [(en)Pt(U-N1,N3,O2,O4)M]4X8 [M = Cu2+, X = Cl (2a), X = (SO4)0.5 (2b), and M = Co2+ (3), Ni2+ (4), Zn2+ (5) with X = (SO4)0.5], in which the heterometals are bound at the exocyclic oxygen atoms of the uracil nucleobases. The structurally characterized heteronuclear compounds show a 1,3-alternate arrangement of the uracil nucleobases. Pt-M contacts are in the range 2.743(2)-2.804(2) Å; the Pt atoms act as weak σ donors to the heterometals. In spite of the high degree of positive charge associated with compounds 2a-5, they do not behave as hosts for anions. This is a consequence of the orientation of the four nucleobases which, in contrast to a cone arrangement, does not produce a sufficiently large cavity for the incorporation of anions.
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  • 86
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 165-168 
    ISSN: 1434-1948
    Keywords: Arsenic ; Imino compound ; Hydrazinoiminoarsane ; Aminoiminoarsane ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dehydrohalogenation of (2,4,6-tri-tert-butylphenylamino)chloro[tris(trimethylsilyl)hydrazino]arsane (3) or [tert-butyl(trimethylsilyl)amino]chloro(2,4,6-tri-tert-butylphenylamino)arsane (4) with DBU yields novel stable compounds containing an As-N double bond, (2,4,6-tri-tert-butylphenylimino)[tris(trimethylsilylhydrazino]arsane) (5) and [tert-butyl(trimethylsilyl)amino](2,4,6-tri-tert-butylphenylimino)arsane (6). The structure of 5 was confirmed by an X-ray structure determination.
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  • 87
    ISSN: 1434-1948
    Keywords: Manganese ; Radicals ; Cyclic dimer complexes ; Exchange coupling parameters ; Spin states ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Temperature-dependent paramagnetic susceptibility data for two cyclic dimer complexes of bis(hexafluoroacetylacetonato)manganese(II) with 5-tert-butyl-1,3-phenylenebis(N-tert-butylaminoxyl) and 4-(N-tert-butyl-N-oxyamino)pyridine have been analyzed to obtain two sets of two intramolecular exchange coupling parameters J1 and J2. A previous model, based on one of these interactions being much weaker than the other, could not be explicitly correlated to these actual exchange-coupling parameters. However, the energy levels of the low-lying spin states were found to be reproduced reasonably well by the approximate method.
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  • 88
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 217-224 
    ISSN: 1434-1948
    Keywords: Reaction mechanisms ; Cyclopalladation ; Acetic acid ; Pd-C bond stability ; Polynuclear species ; Palladium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The processes operating during the synthetic cyclopalladation reactions of imines in acetic acid have been studied from a kinetico-mechanistic point of view. These reactions include a fast initial coordination to the palladium through the N-donor atom of the imine, followed by the proper C-H bond activation to produce the acetato bridged dimeric species. At this point, the lability of the bridging acetato groups, the hydrolysis of the C-Pd bonds, and/or the hydrolysis of C=N exo bonds contribute to the generation of dark red polynuclear compounds. The processes occurring after the C-H activation have been followed kinetically, both from palladium acetate plus imine, and the synthetically pure isolated acetato dimers as starting materials. The kinetic and activation parameters have been found identical within experimental error whatever the starting material was (k323 = 1.5 × 10-4 s-1; ΔH# = 51 kJ mol-1; ΔS# = -163 JK-1 mol-1 ΔV# = +19 cm3 mol-1 for the 4-ClC6H4-CH=N-CH2-C6H5 imine derivative 1a). Acidolysis of C-Pd bonds has been found to occur in these polynuclear species. When alternative monomeric Cbenzylic-Pd bond-containing complexes are possible follow ups of the reactions produce them as final dead-end complexes (k323 = 2.2 × 10-5 s-1; ΔH# = 61 kJ mol-1; ΔS# = JK-1 mol-1 ΔV# ≈ 0 cm3 cm-1 for the [2,4,6-(CH3)3]C6H2-CH=N-CH2-[2-(CH3]C6[H4] imine derivative 3d). The same study has been carried out with primary amines in order to check the validity of the data if C=N bond hydrolysis is taking place in the imine derivatives with exo C=N bonds. For complexes with similar type of metallacycles, the results agree reasonably well with the proposed mechanism [k323 = 1.2·10-4 s-1, ΔH# = 46 kJ·mol-1, ΔS# = -180 J·K-1mol-1, ΔV# = -16 cm3·mol-1 for the polynuclear formation of the C6H5-CH2-NH2 derivative 4e; k323 = 3.0·10-4 s-1, ΔH# = 55 kJ·mol-1, ΔS
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  • 89
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 281-285 
    ISSN: 1434-1948
    Keywords: NMR spectroscopy ; Zeolites ; Al-coordination ; Mordenite ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 27Al 3Q MAS NMR spectroscopy has been applied to study the coordination state of the species giving the 30 ppm Al NMR signal in the 27Al MAS NMR spectrum of activated mordenite materials. From the 27Al 3Q MAS NMR measurements it is evident that the broad peak at 30 ppm in the 27Al NMR spectrum of the mordenite calcined at temperatures up to 600 °C comes mainly from the distorted four-coordinated Al. By simulation a quadrupolar coupling constant of 5.8 MHz was estimated for the distorted tetrahedral Al. For samples calcined at 650 and 700 °C, a small amount of pentacoordinated Al emerges. The majority of the signal, however, arises from distorted tetrahedral Al. A two-step calcination results in a significant contribution of the pentacoordinated Al to the signal at 30 ppm. From the simulated line-shape, a quadrupole coupling constant of 6.2 MHz is obtained for the latter signal. These data show that during the calcination of the mordenite, the coordination environment at the Al centre gradually becomes distorted to give rise to the shoulder at 30 ppm. With the increase of the calcination temperature, pentacoordinated Al species form
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  • 90
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 287-297 
    ISSN: 1434-1948
    Keywords: Enolates ; Nucleophilic additions ; Ruthenium ; S ligands ; Sulfenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of the chiral racemic complex [CpRu(mppe)(SO2)]PF6 (1, mppe = Me2PC2H4PPh2) with diazomethane or -ethane gave the sulfene complexes [CpRu(mppe)(RHC/SO2)]PF6 (R = H, 2a; R = Me, 2b). Treatment of 2a with prochiral enamines or deprotonated β-oxo esters yielded C-C coupling products with 32-60% de. An analog of 2a, [NmcpRu(mppe)(H2C/SO2)]PF6 (8, Nmcp = neomenthylcyclopentadienyl) was prepared in a four-step synthesis starting from LiNmcp and [RuCl2(PPh3)3]. Repeated crystallization of the intermediate [NmcpRu(mppe)Cl] (6) provided diastereomerically pure 6′ which added methylene stereospecifically to give diastereomerically pure 8′. Compound 8 turned out to be much less reactive towards nucleophiles than 2a, but still added deprotonated ethyl 2-methyl-3-oxobutanoate with 44% de. The chiral, enantiomerically pure sulfur dioxide complex [CpRu(chir)(SO2)]PF6 [10, chir = (S,S)-Ph2PCHMeCHMePPh2] was synthesized from [CpRu(chir)Cl] and SO2 and was characterized by X-ray crystallography. Reaction of 10 with diazomethane gave the enantiomerically pure sulfene complex [CpRu(chir)(H2C/SO2)]PF6 (11). Addition reactions of 11 with N-(1-cyclopentenyl)morpholine, as well as with various enolates derived from β-oxo esters or 1,3-diesters proceeded with high yields and 20-90% de. The structure of a diastereomerically pure addition product, [CpRu(chir)(SO2CH2C(Me){C(O)Me}{C(O)OtBu}] (13d′), was determined crystallographically and was shown to have (R) configuration at the quaternary carbon atom. After alkylation of one of the S/O functions, the sulfinate ligand was cleaved from the metal center by ligand substitution with acetonitrile, and the resulting acetonitrile complex 15 was converted back into 10 by treatment with SO2.
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  • 91
    ISSN: 1434-1948
    Keywords: Phosphanylphenolate ; Cyclopentadienylnickel complexes ; Chelates ; Ethylene polymerization ; Crystal structure ; Polymerizations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Diphenylphosphanyl- and 2-alkylphenylphosphanyl-4-methylphenols 1 or their silyl ethers 2 and equimolar amounts of nickelocene react in benzene preferably to give orange-brown diamagnetic cyclopentadienylnickel chelate complexes [η-CpNi(P∩O)] (3). Addition of a second equivalent of 1 or 2 affords (RR) and (SS) diastereoisomers of cis-bis(P∩O-chelates) 4a-c (R = Ph, Me, iPr) or the unsymmetrical cis-bis(P∩O-chelate) 5, whereas with bulkier substituted derivatives 1d or 2d (R = tBu) the second step is hindered or retarded. The reactivity of 1d remains high towards nickel salts in polar solvents, but in contrast to 1a-c, yielding 4, a sparingly soluble green trans-bis(P-O-chelate) nickel complex 6d is formed. Complexes formed in situ from 1 or 2 and Ni(COD)2 in toluene catalyze the polymerization of ethylene. The cyclopentadienyl (P∩O) complexes 3, however, are too stable to be active in this process. The crystal and molecular structure of 3c and 4c are described.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99035_s.pdf or from the author.
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  • 92
    ISSN: 1434-1948
    Keywords: Copper ; Magnetic properties ; Supramolecular chemistry ; Three-dimensional architecture ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel three-dimensional copper(II) compound of the formula [Cu3(btre)5(H2O)2](ClO4)6·H2O (btre = 1,2-bis(1,2,4-triazol-4-yl)ethane) has been synthesized. The structure has been solved at 150 K by single-crystal X-ray analysis. The compound [C30H44Cu3N30O2·6(ClO4)·H2O] crystallizes in the triclinic space group P1bar with a = 12.488(1), b = 13.195(1), c = 19.756(2) Å, α = 78.959(8), β = 84.553(8), γ = 63.869(7)°, V = 2868.4(5) Å3, Z = 2 (trinuclear CuII units), 6484 reflections [I 〉 4σ(Ι)], RF = 0.0581, wR2 = 0.1214. The structure of this coordination polymer consists of a three-dimensional network built up from linear trinuclear CuII cations of formula [Cu3(btre)5(H2O)2]6+. This crystallographically independent unit comprises a linear array of three CuII ions linked by triple N1,N2-1,2,4-triazole bridges, yielding Cu1-Cu2 = 3.893(1) Å and Cu2-Cu3 = 3.889(1) Å. These linear trinuclear CuII units are linked by various pathways involving tridentate and tetradentate bridging btre ligands, which yields an unprecedented three-dimensional network. The CuII ions are weakly antiferromagnetically coupled with J = -1.01(2) cm-1 (based on the Hamiltonian: H = -J[SCu1·SCu2 + SCu2·SCu3] using the expression for the molar magnetic susceptibility S = 1/2 of a linear trinuclear system). The nature and the magnitude of the antiferromagnetic exchange have been discussed on the basis of the structural features.
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  • 93
    ISSN: 1434-1948
    Keywords: Metal-rich antimonides ; Magnetism ; Structure and bonding ; Conductivity ; LMTO ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title compounds can be synthesized in quantitative yields by arc-melting of stoichiometric amounts of HfSb2, Hf and one of the 3d metals V, Cr, Mn, Fe, Co, Ni, and Cu. These antimonides crystallize in a substitution variant of the W5Si3 type, in which one position is statistically mixed, occupied by the 3d metal atom M or the Sb2 atom in different ratios. Within the linear (M,Sb) chain, the M:Sb ratio may vary between 3:1 and 2:3. According to calculations of the electronic structures of Hf10MδSb6-δ with δ = 1, these phases are metallic compounds stabilized by strong Hf-Hf, Hf-M, and Hf-Sb bonds, and to a smaller extent by bonding interactions within the linear (M,Sb) chain. The metallic character was confirmed by measurements of the electrical resistivity and the magnetism of selected samples. Whereas Pauli paramagnetism was observed experimentally for M = V, Co, and Ni, Hf10FeSb5 is apparently the only phase with localized magnetic moments and magnetic coupling. This is in agreement with the magnetic ground state obtained solely for the ordered structure model of Hf10FeSb5 with spin-polarized calculation within the local spin density approximation.
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  • 94
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 505-512 
    ISSN: 1434-1948
    Keywords: Ion-molecule reactions ; Mass spectrometry ; Allene ; Germanium ; Silicon ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase ion chemistry of germane/allene and silane/allene mixtures has been studied, with the aim of obtaining information on the experimental conditions leading to the formation of clusters of increasing size containing Ge or Si bonded to carbon atoms. Mechanisms of ion/molecule reactions have been elucidated by ion-trap mass spectrometry using single and multiple isolation steps. Rate constants for the most important reactions have been determined experimentally and compared with collisional rate constants. The germane/allene mixtures display a low reactivity and the most abundant germanium and carbon containing ion is GeCH3+. However, chain propagation proceeds after the first nucleation step, even if rather slowly, with the formation of large clusters such as Ge4C3H3+ at low abundance. In contrast, the silane/allene mixtures are very reactive and many different processes are observed, with the formation of several silicon and carbon containing ions with appreciable efficiency. Chain propagation proceeds mainly through reactions of silicon-containing ions with allene molecules and the subsequent formation of large clusters such as Si3C3H5+ and Si4C3H7+.
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  • 95
    ISSN: 1434-1948
    Keywords: Tin ; Nucleotides ; NMR spectrometry ; Mass spectroscopy ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interactions between diethyltin dichloride and 5′-CMP, 5′-dCMP, and 5′-UMP in aqueous solution were investigated by multinuclear 1D and 2D NMR techniques including 119Sn, 15N and 31P nuclei. These studies were combined with electrospray mass spectrometry, infrared spectroscopy, solid state 13C, 31P and 117Sn CP-MAS NMR, and elemental analysis. As demonstrated by 31P-1H HOESY spectroscopy, the diethyltin moiety interacts with the phosphate group of the pyrimidic mononucleotides in the pH range 0.5-3.5. Compound 8 (X = Cl), the solid isolated in this pH range from 5′-CMP, contains two tin atoms bridged by one oxygen and one chlorine atom, each tin atom being linked to the phosphate group of a nucleotide moiety. For 5′-UMP the solid isolated (12) has a dimeric structure with two different tin atoms; it can be formed by dimerization of compound 11 with the elimination of two water molecules. As demonstrated by 1H-119Sn HMQC correlation NMR data and the 2J(119Sn-O-117Sn) coupling constant of 156 Hz, the diethyltin moiety reacts with the O(2′) and O(3′) oxygen atoms of the nucleotides to form a dimeric diethyldioxastannolane at pH 〉 9.0. Between pH 5.0 and 9.0, no evidence for any interaction between the diethyltin moiety and the nucleotides was found.
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  • 96
    ISSN: 1434-1948
    Keywords: Coordination chemistry ; Gallium(III) ; Dynamik 19F NMR ; EXSY ; Kinetics of ligand exchange ; Bailar and Rây-Dutt mechanisms ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of intramolecular rearrangement of the meridional isomer of the metal tris-chelate complex [Ga(fox)3, fox = 5-fluoro-8-hydroxyquinoline] in DMF solution were measured using 1D NMR line shape analysis and 2D EXSY spectra. The rates of exchange kab, kbc and kac between the three non-equivalent ligands a, b and c were determined. The values of the activation parameters were obtained. ΔH
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  • 97
    ISSN: 1434-1948
    Keywords: Pyrrolizinato complexes ; Tetracyanoethylene ; Phthalocyanines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complexes of NiII, CuII, ZnII, and CoIII containing the 1,2,6,7-tetracyano-3,5-dihydro-3,5-diiminopyrrolizinide (L) and the 2,4-tert-butylacetylacetonide (DPM) ligands have been synthesized and characterized. The absorption optical spectra of these species and of the corresponding ML2 complexes in coordinating solvents are compared with those of metal-phthalocyanines (MPc) and hydrogen-phthalocyanine (H2Pc), respectively. The comparison shows a close similarity, especially for the nickel-containing species, in the low-energy spectral region where the first π→π* transitions occur (Q band). The Q band position of the pyrrolizinato complexes is much more dependant on the metal than is the case for MPc. For the same metal, the Q band position is also dependant on the M-N bond lengths in the molecular plane. For M = Ni, a reduction of this distance causes a red-shift of the Q band and a decrease of its maximum intensity. These conclusions are based on the X-ray molecular structure of the solvent-free NiL(DPM) complex and its pyridine solvate NiL(DPM)(Pyr)2 · 2 Pyr and on their solvatochromism. A symmetry-based correlation diagram between the frontier orbitals of the pyrrolizinato-complexes and the phthalocyanines is proposed.
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  • 98
    ISSN: 1434-1948
    Keywords: Mesoporous materials ; MCM-41 ; MCM-48 ; Immobilisation ; Solid-state NMR ; Heterogeneous catalysis ; Titanium ; Titanocenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Titanium(IV)-grafted mesoporous silicas have been prepared by diffusion of an excess of the ansa-bridged titanocene [SiMe2(η5-C5H4)2]TiCl2 into the channels of hexagonal MCM-41 and cubic MCM-48 in dichloromethane or tetrahydrofuran at room temperature. The choice of solvent determines the course of the reaction and hence the activity of the resulting materials as catalysts in the catalytic epoxidation of cyclooctene with tert-butylhydroperoxide. Magic-angle spinning (MAS) NMR (13C, 29Si) spectroscopy was used to characterise the local environment of the surface-bound titanium active sites. When dichloromethane is used, the dominant species anchored to the surface are isolated ansa-bridged titanocene fragments. When THF is used, the [SiMe2(η5-C5H4)2] unit is lost with the concomitant formation of surface-bound TiIV species coordinated by THF molecules. These materials showed the best catalytic performance per Ti atom for the conversion of cyclooctene. All materials were further characterised by means of elemental analysis, powder X-ray diffraction (XRD), N2 adsorption and FTIR spectroscopy.
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  • 99
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 559-565 
    ISSN: 1434-1948
    Keywords: Macrocyclic ligands ; Copper ; EPR spectroscopy ; Electronic spectrophotometry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copper(II) mononuclear complexes with the polyazamacrocyclic ligands NOTA (1,4,7-triazacyclononane-N,N′,N″triacetate), DOTA (1,4,7,10-tetraazacyclo-dodecane-N,N′,N″,N″′-tetraacetate), NOTP [1,4,7-triazacyclononane-N,N′,N″-tris(methylenephosphonate)] and DOTP [1,4,7,10tetraazacyclododecane-N,N′,N″,N‴-tetrakis(methylenephosphonate)] were characterised in aqueous solution by electronic absorption spectrophotometry and electron paramagnetic resonance (EPR) spectroscopy. While two isomeric species were detected by EPR spectroscopy in frozen samples of the polycarboxylate complexes, only one complex form was found for the poly(methylenephosphonate) systems. The results obtained are in accordance with a six-coordinate pattern for the metal centre, yielding tetragonally distorted complexes in solution, in agreement with previously reported studies on CuII complexes, both in solution and in the solid state.
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  • 100
    ISSN: 1434-1948
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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