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  • Articles: DFG German National Licenses  (2,820)
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  • Articles: DFG German National Licenses  (2,820)
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  • 101
    ISSN: 1615-6706
    Keywords: Schlüsselwörter: Liquordynamik ; Aquädukt ; Quantifizierung ; MRT ; Phasenkontrast ; Normalwerte ; Key Words: CSF dynamics ; Aqueduct ; Quantification ; MRI ; Phase contrast ; Normal values
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Abstract: With the 2D-phase-contrast technique the volume flow of the CSF via the cerebral aqueduct can be quantified by MRI-means. In this study the stroke volume of CSF via the aqueduct per cardiac cycle (SVcc) is used to measure the extent of the volume flow. Normative values for the SVcc are not yet defined, however, they are indispensable for the clinical utility of this non-invasive method. The aim of the presented investigation is to evaluate, if the interthalamic width of the third ventricle is useful as a reference system for the extent of the SVcc via the aqueduct and if a normal CSF-flow can be defined. Hundred and seven patients (56 female, 51 male; age distribution 8 to 89 years) without clinical or imaging findings of a CSF-flow disturbance were examined on a standard 0.5 T MRI-scanner (Gyroscan, Philips). The measurements of the SVcc via the aqueduct were performed in a single slice perpendicular to the aqueduct in the level of its median third with a retrospective cardial-gated quantitative 2D-phase-contrast sequence. The interthalamic width of the third ventricle was measured in a transversal slice (bicommissural orientation, standard T1-weighted spin-echo sequence) in the level of the upper margin of the tectorial membrane. In 83 patients with a normal heart rate and without any further abnormalities in their imaging studies the SVcc is essentially dependent (r = 0.822) on the interthalamic width of the third ventricle (between 1 and 16 mm). Eleven patients with either a subcortical atrophy without leucencephalopathy, megacisterna magna, Dandy-Walker variant or bradycardia showed a significant increase of the SVcc (p 〈 0.05). On the other hand a significant decrease of the SVcc (p 〈 0.05) is seen in 13 patients with either tachycardia, Arnold-Chiari Type-1 malformation, relative aqueductal stenosis and/or severe periventricular leucencephalopathy. These results are in good agreement with the current conceptions on the physiology of the CSF-flow. As the above mentioned criterias of influence have ho pathological significance concerning a CSF-flow disturbance requiring therapy, we used the linear regression with y = B1*× +b0 (b1 = 22.2 ± 2.9; b0 = 43,5 ± 21.1) in all 107 patients to evaluate the extent of the SVcc (y) versus the interthalamic width of the third ventricle (x). This correlation offers the possibility to differentiate a hyperdynamic (above +3 standard error SE), a hypodynamic (below −3 SE) and a normodynamic (between ± 3 SE) CSF-flow via the cerebral aqueduct for the first time. Additional imaging findings and the heart rate must find their influence in the evaluation.
    Notes: Zusammenfassung: Mit Hilfe der 2D-Phasenkontrasttechik kann der Volumenfluss des Liquors über dem Aquädukt magnetresonanztomographisch quantifiziert werden. Als Maß für die Höhe des Volumenflusses dient in vorgestellter Untersuchung das Schlagvolumen pro Herzzyklus (SVcc). Normwerte für die Höhe des SVcc konnten bislang nicht definiert werden. Sie sind jedoch für eine klinische Nutzung dieses nichtinvasiven Verfahrens unerläßlich. Ziel vorliegender Untersuchung ist es zu prüfen, ob die interthalamische Weite des dritten Ventrikels als Bezugssystem für die Höhe des SVcc über dem Aquädukt geeignet ist und sich ein normaler Liquorfluss definieren läßt. Die Untersuchungen erfolgten bei 107 Patienten (56 Frauen, 51 Männer im Alter von acht bis 89 Jahren) ohne klinische und bildmorphologische Hinweise auf eine Liquorzirkulationsstörung an einem Standardsystem 0,5 T (Gyroscan, Fa. Philips). Die Messung des SVcc über dem Aquädukt wurde in einer Eizelschicht senkrecht zum Aquädukt in Höhe des mittleren Drittels mit einer retrospektiv kardial getriggerten 2D-quantitativen Phasenkontrastsequenz durchgeführt. Die Messung der interthalamischen Weite des dritten Ventrikels erfolgte im Transversalschnitt (Bikommissuralebene, Standard-T1-gewichtete SE-Sequenz) in Höhe des Oberrandes der Lamina tecti. Für 83 kardial normofrequente Patienten ohne zusätzliche bildmorphologische Auffälligkeiten wird die Höhe des SVcc maßgeblich von der interthalamischen Weite des dritten Ventrikels (1 bi 16 mm) bestimmt (r = 0,822). Bei elf Patienten mit einer subkortikal betonten Atrophie ohne Leukenzephalopathie, Megacisterna magna, Dandy-Walker-Variante oder Bradykardie ist das SVcc signifikant erhöht (p 〈 0,05). Dagegen ist das SVcc für 13 Patienten mit Tachykardie, Arnold-Chiari-Malformation Typ 1, relativer Aquäduktestenose und/oder fortgeschrittener periventrikulärer Leukenzephalopathie signifikant erniedrigt (p 〈 0,05). Diese Ergebnisse lassen sich gut mit den geltenden Vorstellungen über die Physiologie des Liquorflusses in Einklang bringen. Da den vorgenannten Einflusskriterien keine pathologische Bedeutung hinsichtlich einer therapiebedürftigen Liquorzirkulationsstörung beigemessen werden kann, nutzen wir zur Bewertung der Höhe des SVcc (y) gegenüber der interthalamischen Weite des dritten Ventrikels (x) die lineare Regression mit y = b1*× + b0 (b1 = 22,2 ± 2,9; b0 = 43,5 ± 21,1) für alle 107 Patienten. Diese Beziehung gibt erstmals die Möglichkeit, einen hyperdynamen (〉 +3 SE), hypodynamen (〈 −3 SE) und normodynamen (in den Grenzen ± 3SE) Liquorfluss über dem Aquädukt zu differenzieren. In die Bewertung müssen das Vorliegen zusätzlicher bildmorphologischer Einflussfaktoren und die Höhe der Herzfrequenz einfließen.
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  • 102
    ISSN: 1615-6706
    Keywords: Schlüsselwörter: Medulloblastom ; Pubertas praecox ; MRT ; Kontrastmittel ; Key Words: Medulloblastoma ; Subarachnoid metastases ; Precocious puberty ; MRI ; Contrast enhancement
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Abstract: Medulloblastoma, the most frequent pediatric brain tumor, has known propensity for subarachnoid dissemination. Spinal metastases indicate a poor prognosis. Intraventricular spread is much less common. We report a case of primary intraventricular dissemination with precocious puberty as the first clinical symptom due to a metastasis at the infundibulary stalk. This has not been reported so far as initial symptom of a medulloblastoma. Furthermore, we encountered an unusually mild contrast enhancement of the spinal and intraventricular metastases. Delayed scanning after contrast administration and FLAIR sequences proved to be particularly valuable in this case.
    Notes: Zusammenfassung: Medulloblastome des Kleinhirns sind die häfigsten malignen Hirntumoren im Kindesalter. Ihre Neigung zur Ausbreitung im Subarachnoidalraum ist bekannt und Prognose bestimmend. Wir berichten über den ungewöhnlichen Fall eines Medulloblastoms mit ausgeprägter intraventrikulärer Aussaat. Eine Metastase im Reccessus infundibularis führte hierbei zum Auftreten einer Pubertas praecox als initiales Krankheitssymptom, eine Beobachtung, die bisher nicht beschrieben wurde. Bemerkenswert war zudem die ungewöhnlich schwache Kontrastmittelaufnahme der intraventrikulären und spinalen Metastasen. Für die Diagnostik erwiesen sich FLAIR-Sequenzen und Spätaufnahmen nach Kontrastmittelgabe als besonders wertvoll.
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  • 103
    ISSN: 1615-6706
    Keywords: Schlüsselwörter: Vena ophthalmica superior ; Thrombose ; Sinus caverosus ; Computertomographie ; Kernspintomographie ; Key Words: Superior ophthalmic vein ; Thrombosis ; Sinus cavernosus ; CT ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Abstract: A 65-year-old woman with persistant headache since a few weeks is presented. The day before hospitalization there was a sudden onset of protrusio bulbi and progredient swelling of the soft-tissue of the left eye. In the clinical examination left side protrusio bulbi, double-vision, chemosis and swelling of the eye-lid were found. Blood sample showed an elevation of inflammation indicators. MRI and CT revealed a thrombosis of the left superior ophthalmic vein with partial thrombosis of the left cavernous sinus.
    Notes: Zusammenfassung: Eine 65-jährige Patientin stellt sich mit seit Wochen bestehenden Kopfschmerzen vor. Am Tag vor der Aufnahme war morgens akut eine Protrusio bulbi mit einem periorbitalen Ödem aufgetreten. Klinisch fanden sich eine Protrusio bulbi mit Chemosis und Oberlidschwellung links, Doppelbildern sowie einer Erhöhung der Entzündungsparameter. Kernspintomographisch und computertomographisch ließ sich eine Thrombose der Vena ophthalmica superior links mit Teilthrombose des linken Sinus cavernosus nachweisen.
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  • 104
    Electronic Resource
    Electronic Resource
    Springer
    European journal of applied physiology 83 (2000), S. 363-369 
    ISSN: 1439-6327
    Keywords: Key words Achilles tendon moment arm ; MRI ; Maximum voluntary contraction ; In vivo ; Tendon excursion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The aim of the present study was to estimate and compare in vivo measurement-based Achilles tendon moment arm lengths at rest and during isometric plantarflexion maximum voluntary contraction (MVC) using the centre-of-rotation (COR) and the tendon-excursion (TE) methods. Both methods were based on morphometric analysis of sagittal-plane magnetic resonance images of the foot. Using the COR method, moment arms were obtained at ankle angles from 15° of dorsiflexion to 30° of plantarflexion in steps of 15°, digitizing the perpendicular distance from a moving centre of rotation in the tibio-talar joint to the Achilles tendon action line. The TE method was based on measurement of calcaneal displacement along the tibial axis during 15° rotations of the ankle joint, from 30° of dorsiflexion to 45° of plantarflexion. The two methods gave similar estimations at rest varying from 4.3 to 5.6 cm. Using the COR method, the Achilles tendon moment arm during MVC was larger by 1–1.5 cm (22–27%, P 〈 0.01) than the respective resting value. In contrast, no difference (P 〉 0.05) was found between the resting and MVC moment arm estimations of the TE method. The disagreement in moment arms during MVC may be attributed to differences in the assumptions made between the two methods. The TE method has more limitations than the COR method and its estimations during MVC should be treated with caution. Resting Achilles tendon moment arm estimations of the COR method should be multiplied by 1.22–1.27 when maximal isometric plantarflexion joint moments, musculotendon forces and stresses are predicted using modelling.
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  • 105
    ISSN: 1573-7373
    Keywords: SCLC ; brain matastases ; neurologic asympotomatic ; MRI ; prophylactic radiotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Purpose. In this study we evaluated the usefulness of MR-imaging in the detection of asymptomatic brain metastases (BM) at the initial diagnosis in patients with small cell lung cancer (SCLC) and studied the follow-up of these patients. Patients and methods. One-hundred and twenty-five patients with SCLC were investigated with MR-imaging. Results. In 112 patients with normal neurological findings, MR-imaging of the brain demonstrated BM in 17 patients (15%). Six of these 17 patients were therefore upgraded to extensive disease (ED). Two of these 17 patients died during chemotherapy because of progressive disease and 3 patients became neurologic symptomatic with progressive disease on MR-imaging of the brain. After completion of chemotherapy a repeated MR-imaging of the brain in the remaining 12 patients showed 1 complete remission, 4 partial remission and 7 progressive disease of the BM. Conclusion. This study showed that at presentation an unexpectedly high percentage of SCLC patients had asymptomatic BM on MR-imaging. We propose that MR-imaging of the brain should be included in the staging of SCLC patients as well for staging, prognosis and therapy.
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  • 106
    ISSN: 1573-7373
    Keywords: astrocytoma ; 201thallium SPECT ; MRI ; MR spectroscopy ; chemotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Purpose To compare chemotherapy treatment monitoring in astrocytoma by 201thallium single photon emission computed tomography (SPECT) and photon magnetic resonance spectroscopy (1H-MRS) with magnetic resonance imaging (MRI), and to evaluate the influence of morphological tumor changes on cerebral 201thallium uptake and metabolic changes in 1H-MRS. Materials and methods Six patients with highly malignant astrocytomas were followed with quantitative 201thallium SPECT, MRI, and 1H-MRS during chemotherapy. Maximum follow-up included six examinations per patient by either method during 18 months. Criteria were set for: (1) regression (≥ 25% tumor reduction), (2) status quo (〈 25% reduction and 〈 25% increase), and (3) progression of disease (≥ 25% tumor increase). Results were compared with the clinical state of disease. Changes of tumor volume, contrast enhancement, necrosis, hemorrhage and edema on MRI were compared to changes in 201thallium uptake volumes and 1H-MRS metabolite ratios. Results Six patients were followed with a total of twenty-four examinations with 201thallium SPECT, MRI and 1H-MRS, respectively, between February 1997 and October 1998. Five patients developed clinical progression of disease, 4 out of 5 cases showed SPECT progression, 4 out of 5 cases MRI progression, and 1 out of 2 interpretable cases 1H-MRS progression at final assessment before clinical deterioration. During the phase of clinically stable disease; (A) the criterion for regression or status quo was met in 10 out of 13 assessments with SPECT, 11 out of 13 with MRI, and 8 out of 9 interpretable 1H-MRS; (B) the criterion for progression was met in 3 out of 13 with SPECT, 2 out of 13 with MRI, and 1 out of 9 interpretable 1H-MRS. The accuracy of SPECT, MRI, and 1H-MRS in identifying changes of tumor burden concordant with patients' clinical course was 78%, 83%, and 82%, respectively. SPECT regression was associated with MRI decrease of tumor size, contrast enhancement, edema and hemorrhage. SPECT progression was associated with MRI increase of the same parameters and the increase of necrosis. 1H-MRS regression was associated with decrease of edema. 1H-MRS progression was associated with increase of tumor size, hemorrhage, and increase or decrease of contrast enhancement. Conclusions Both 201thallium SPECT and 1H-MRS evaluation showed sensitivity for detection of astrocytoma progression. We did not find a higher accuracy of SPECT or MRS than of MRI in astrocytoma chemotherapy monitoring. Treatment induced MRI changes were associated with 201thallium uptake variations. 1H-MRS was difficult to apply for astrocytoma treatment monitoring. Improvements regarding size of measurement area such as multivoxel MRS and fat suppression pulses appeared desirable, and also the use of functional techniques with superior resolution such as dual isotope SPECT. However, our results suggest that 201thallium SPECT and 1H-MRS can provide additional information to MRI for chemotherapy efficacy evaluation in selected cases.
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  • 107
    Electronic Resource
    Electronic Resource
    Springer
    Journal of neuro-oncology 47 (2000), S. 195-210 
    ISSN: 1573-7373
    Keywords: MRI ; spinal cord ; tumor ; intramedullary
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The advent of MRI has significantly changed the diagnosis of spinal cord tumors. Standard imaging provides excellent localization and characterization of the tumor in a noninvasive fashion. Exact histologic diagnosis of the two most common tumors, ependymoma and astrocytoma, remains elusive but there are some suggestive imaging characteristics. It is hoped that some of the newer MR imaging sequences will improve characterization of the tumor and thereby influence therapy. Several of these pulse sequences are already used routinely in brain imaging. Evaluation of new imaging sequences in the spine has lagged behind brain MR imaging, mainly due to technical factors. Work on animal spine models and extrapolation from brain imaging studies suggest that it is only a matter of time before some of these techniques become clinically relevant.
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  • 108
    ISSN: 1573-7373
    Keywords: brain ; brain tumors ; MRI ; MR spectroscopy ; diffusion imaging ; glioma
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract This study sought to correlate quantitative presurgical proton magnetic resonance spectroscopic imaging (1H- MRSI) and diffusion imaging (DI) results with quantitative histopathological features of resected glioma tissue. The primary hypotheses were (1) glioma choline signal correlates with cell density, (2) glioma apparent diffusion coefficient (ADC) correlates inversely with cell density, (3) glioma choline signal correlates with cell proliferative index. Eighteen adult glioma patients were preoperatively imaged with 1H-MRSI and DI as part of clinically-indicated MRI evaluations. Cell density and proliferative index readings were made on surgical specimens obtained at surgery performed within 12 days of the radiologic scans. The resected tissue location was identified by comparing preoperative and postoperative MRI. The tumor to contralateral normalized choline signal ratio (nCho) and the ADC from resected tumor regions were measured from the preoperative imaging data. Counts of nuclei per high power field in 5–10 fields provided a quantitative measure of cell density. MIB-1 immunohistochemistry provided an index of the proportion of proliferating cells. There was a statistically significant inverse linear correlation between glioma ADC and cell density. There was also a statistically significant linear correlation between the glioma nCho and the cell density. The nCho measure did not significantly correlate with proliferative index. The results indicate that both ADC and spectroscopic choline measures are related to glioma cell density. Therefore they may prove useful for differentiating dense cellular neoplastic lesions from those that contain large proportions of acellular necrotic space.
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  • 109
    ISSN: 1615-6692
    Keywords: Key Words Cardiac imaging ; MRI ; Heart ; Ventricular function ; Schlüsselwörter Kardiale Bildgebung ; Magnetresonanztomographie ; Herz ; Ventrikelfunktion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Die kardiale Dysfunktion ist eine der Hauptursachen kardiovaskulärer Morbidität und Mortalität. Eine genaue und reproduzierbare Bestimmung der Herzfunktion ist essentiell für die Diagnosestellung, Prognoseabschätzung und Beurteilung des Therapieeffekts beim einzelnen Patienten. Die kardiovaskuläre Magnetresonanztomographie (CMR) bietet eine Messmethode für die globale und regionale Herzfunktion, die nicht nur genau und reproduzierbar, sondern auch nichtinvasiv, ohne ionisierende Strahlung und unabhängig von geometrischen Annahmen und einem akustischen Fenster ist, das den Einsatz der Echokardiographie limitiert. Mit der Verfügbarkeit schnellerer MR-Scanner und automatisierter Analysesysteme sowie mit zunehmender Verbreitung und reduzierten Kosten wird CMR bald den Referenzstandard für die Messung der Herzfunktion darstellen.
    Notes: Abstract Cardiac dysfunction is a major cause of cardiovascular morbidity and mortality. Accurate and reproducible assessment of cardiac function is essential for the diagnosis, the assessment of prognosis and evaluation of a patient's response to therapy. Cardiovascular Magnetic Resonance (CMR) provides a measure of global and regional function that is not only accurate and reproducible but is noninvasive, free of ionising radiation, and independent of the geometric assumptions and acoustic windows that limit echocardiography. With the advent of faster scanners, automated analysis, increasing availability and reducing costs, CMR is fast becoming a clinically tenable reference standard for the measurement of cardiac function.
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  • 110
    Electronic Resource
    Electronic Resource
    Springer
    Herz 25 (2000), S. 365-383 
    ISSN: 1615-6692
    Keywords: Key Words Congenital heart disease ; MRI ; Blood flow ; MRA ; Postoperative ; Pulmonary arteries ; Schlüsselwörter Kongenitale Herzerkrankung ; MRT ; Blutfluss ; MR-Angiographie ; Postoperativ ; Pulmonalarterien
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Weltweit werden jährlich etwa 1,5 Millionen Kinder mit kongenitalen Herzerkrankungen (CHD, congenital heart disease) geboren. Durch Verbesserung der verschiedenen chirurgischen und interventionellen Techniken ist die Überlebensrate von CHD-Patienten drastisch gestiegen. Immer mehr Patienten mit postoperativen Residuen, Folgezuständen und Komplikationen benötigen eine umfassende Nachsorge. Die Darstellung und Quantifizierung morphologischer und funktioneller kardiovaskulärer Anomalien erfordern zuverlässige und vorzugsweise nichtinvasive bildgebende Verfahren. Die Röntgenkontrastangiokardiographie, der bisherige Goldstandard, eignet sich nicht zur wiederholten Anwendung. Die transthorakale Echokardiographie (TTE) ist die meistverwendete nichtinvasive Methode, doch bei älteren Patienten, insbesondere mit komplexen oder operativ behandelten Malformationen, sind die damit gewonnenen Informationen unter Umständen unbefriedigend. Narben-, Knochen- und Lungengewebe sowie Thoraxdeformitäten können mit dem Schallfenster interferieren. Die transösophageale Echokardiographie (TEE) liefert bei Erwachsenen mit verschiedenen CHD-Formen eindeutig einen weitaus besseren Bildausschnitt, ist jedoch als semiinvasiv einzustufen. Bei Kleinkindern ist die TEE für die auf Intensivstationen und in Operationssälen erforderliche unmittelbare prä- und postoperative Überwachung inzwischen unentbehrlich. Die Kernspintomographie (Magnetresonanztomographie, MRT) hat sich zu einem klinischen nützlichen Verfahren zur Untersuchung des Herzens entwickelt, vor allem bei angeborenen Fehlbildungen. Sie gilt heute als etablierte nichtinvasive Methode, mit der sich die Anatomie des Herzens in jeder gewünschten Ebene mit hoher Auflösung und naturgetreuen Kontrast zwischen kardialen Strukturen und strömendem Blut darstellen läßt. Das konventionelle Spin-Echo eignet sich hervorragend zur morphologischen Beurteilung, liefert jedoch nicht unbedingt funktionelle Informationen. Die durch neuere Impulssequenzen mögliche funktionelle Analyse verleiht der MRT ihren besonderen Wert. Mehrere dieser neuen MRT-Verfahren werden gegenwärtig klinisch eingesetzt. Die Gradienten-Echo-MRT liefert ein Bild des Blutflusses. Mit ihr können Stenosen, Regurgitation oder Shunts aufgrund der durch diese hämodynamischen Läsionen verursachten Strömungsturbulenzen entdeckt werden. Außerdem ermöglicht die Gradienten-Echo-MRT eine fortlaufende Schleifendarstellung der Ventrikelwandbewegung und eine Quantifizierung der Kammerfunktion. Mit der quantitativen Phasenkontrast-MR-Angiographie lassen sich Blutströmungsgeschwindigkeit und Volumendurchfluss in den mittleren und großen Gefäßen messen. Diese Besonderheit der MRT läßt sich zur Quantifizierung von Stenosen, Regurgitation, intrakardialen Shunts und des differentiellen pulmonalen Blutstroms nutzen. Vor allem ihre Fähigheit zur Messung des Volumendurchflusses ist ein klarer Vorteil der MRT. Die kontrastverstärkte MR-Angiographie ist besonders nützlich zur Darstellung der Pulmonalarterienäste und des Aortenbogens. Pulmonaler Blutfluss, rechtsventrikuläre Funktion, pathologische Aortenbefunde und Fontan-Umgehungskreislauf sind u. a. hochinteressante Fragestellungen, die mit multifunktioneller MRT untersucht wurden. Bei Patienten mit Pulmonalstenose oder Fallot-Tetralogie lassen sich mittels MRT Morphologie und Schwere jeder pulmonalen (Rest-)Stenose beurteilen, die rechtsventrikuläre Hypertrophie bewerten sowie eine postoperative Insuffizienz der Pulmonalklappe oder ventrikuläre Dysfunktion quantifizieren. Bei Patienten, die wegen Koarktation operiert wurden, kann die Morphologie von Rest- oder Restenosen MR-tomographisch mit Hilfe von Spin-Echo-Bildern und der kontrastverstärkten MR-Angiographie des Aortenbogens beurteilt werden. Die quantitative Phasenkontrastangiographie erlaubt zusätzlich, den Druckgradienten über der Stenose und das Ausmaß des Kollateralflusses zu bestimmen. Patienten mit Transposition der großen Arterien werden in der Regel mit Umkehroperationen auf Vorhofebene behandelt. Eine Dysfunktion des rechten systemischen Ventrikels ist bei diesen Patienten eine wesentliche Frage, die mit funktionellen MRT-Verfahren untersucht wurde. Andere Komplikationen nach Vorhofumkehroperation wie Obstruktionen im pulmonalen oder systemisch-venösen Kreislauf lassen sich mit der Gradienten-Echo-MRT mühelos aufdecken. Der Fongan-Umgehungskreislauf bleibt nach wie vor ein faszinierendes, in vielerlei Hinsicht noch nicht völlig verstandenes Thema. Zahlreiche Modifikationen der ursprünglichen Fontan-Operation wurden eingeführt, mit jeweils eigenen hämodynamischen Charakteristika. Zweifellos kann die kombinierte morphologisch-funktionelle MRT zur Entwicklung weiterer Verbesserungen des Fontan-Verfahrens beitragen. Trotz aller technischen Verbesserungen, insbesondere der Einführung des Atemanhalteverfahrens, bleibt die MRT nach wie vor eine Ergänzung zu Echokardiographie und Angiokardiographie. Verfügbarkeit, Ortsgebundenheit und die bei Säuglingen und Kindern erforderliche Sedierung sind bekannte Hindernisse. Nicht zuletzt gilt es, gegen die relativ begrenzte Einbeziehung von Kardiologen in die MRT-Abteilung und die eingeschränkte Verfügbarkeit von Radiologen mit Erfahrung in CHD anzugehen, um die MRT zu einem “vollwertigen Mitglied im Klub” der bildgebenden Verfahren bei CHD zu machen.
    Notes: Abstract With the increasing number of patients surviving after therapeutic intervention for congenital heart disease (CHD), accurate and frequent follow-up of their morphologic and functional cardiovascular status is required, preferably with a noninvasive imaging technique. Echocardiography, either transthoracic or transesophageal, has been the first choice for this purpose, and will probably keep that status, at least in a large segment of the CHD spectrum. Magnetic resonance imaging (MRI) is an established method for high-resolution visualization of cardiovascular morphology. In the past decade, newer MRI techniques have been developed that allow functional evaluation of CHD patients. Particularly the introduction of breath-hold imaging, contrast-enhanced MRA and user-friendly computer software for image analysis may move functional MRI of CHD from the science laboratory to clinical use. It is already evident that MRI is superior to echocardiography in certain areas of limited echocardiographic access, such as the pulmonary artery branches and the aortic arch in adult patients. But MRI has also a unique potential for accurate volumetric analysis of ventricular function and cardiovascular blood flow, without any geometric assumptions. If supported by increased cooperation between cardiologists and radiologists, MRI will grow into a useful noninvasive imaging tool that, together with echocardiography, will obviate the need for invasive catheter studies for diagnostic purposes.
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  • 111
    ISSN: 1434-3924
    Keywords: Schlüsselwörter Arthroskopie ; Klinische Untersuchung ; Kniegelenk ; MRT ; Key words Arthroscopy ; Clinical examination ; Knee ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Summary Magnetic resonance imaging (MRI) is used frequently in the diagnosis of knee injuries. The aim of this study was to compare the accruracy of MRI and clinical examination in diagnosing meniscal and cruciate ligament tears. Between January 1997 and June 1998, a total of 883 patients had undergone knee joint arthroscopy, operated on by one orthopedic surgeon. Of these, 144 patients had a preoperative MRI (group 1). This group was compared with 309 patients who had undergone arthroscopy without MRI between January 1997 and June 1997 (group 2). Sensitivity, specificity and accuracy for tears of the medial meniscus were 80.6%/58.8%/72.9% in group 1 and 83.3%/78.5%/80.3% in group 2, respectively, for tears of the lateral meniscus 44.4%/88.9%/83.3% in group 1 and 60.6%/98.8%/92.5% in group 2 and for tears of the anterior cruciate ligament 58.1%/92.0%/¶84.7% in group 1 and 80.1%/96.6%/¶89.6% in group 2. This study demonstrates that an experienced orthopedic surgeon can rely on the clinical diagnosis and decide whether arthroscopy is necessary in most cases without MRI. He will find intraarticular pathology in almost all cases if arthroscopy is performed. MRI should be reserved for special cases and should not be performed without first conducting a thorough clinical examination. The orthopedic surgeon should decide whether MRI is needed.
    Notes: Zusammenfassung Mit zunehmender Häufigkeit wird beim Verdacht auf einen Kniebinnenschaden die Magnetresonanztomographie (MRT) eingesetzt. Ziel der vorliegenden Arbeit war es, die Treffsicherheit von MRT und klinischer Untersuchung bei der Diagnose von Meniskusläsionen und Kreuzbandverletzungen zu vergleichen und daraus zu schlussfolgern, wann ein MRT am Kniegelenk indiziert ist. Vom 1.1.1997 bis zum 30.6.1998 wurden 883 Kniegelenkarthroskopien durchgeführt. Bei 144 Kniegelenken lag präoperativ ein MRT vor (Gruppe 1). Dieser Gruppe wurde eine Vergleichsgruppe, bestehend aus allen vom 1.1.1997 bis zum 30.6.1997 arthroskopierten Kniegelenken ohne präoperatives MRT (n = 309) gegenübergestellt (Gruppe 2). Sensitivität, Spezifität und Präzision betrugen für den medialen Meniskus 80,6%, 58,8% bzw. 72,9% in Gruppe 1 und 83,3%, 78,5% bzw. 80,3% in Gruppe 2, für den lateralen Meniskus 44,4%, 88,9% bzw. 83,3% in Gruppe 1 und 60,6%, 98,8% bzw. 92,5% in Gruppe 2 und für das vordere Kreuzband 58,1%, 92,0% bzw. 84,7% in Gruppe 1 und 80,1%, 96,6% bzw.89,6% in Gruppe 2. Mit einer sorgfältigen klinischen Untersuchung können in Verbindung mit Standardröntgenaufnahmen in den meisten Fällen die Diagnose und damit die Indikation zur Arthroskopie mit ausreichender Sicherheit gestellt werden. Die Magnetresonanztomographie sollte Spezialindikationen vorbehalten bleiben und durch den Operateur veranlasst werden.
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  • 112
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    Arthroskopie 13 (2000), S. 132-137 
    ISSN: 1434-3924
    Keywords: Schlüsselwörter Qualitätssicherung ; Knorpeldefekte ; MRT ; Scores ; Keywords Quality control ; Cartilage repair ; MRI ; Clinical scores
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Most procedures currently in use for the treatment of full thickness cartilage defects lack solid data as a proof of quality. Various techniques for quality control are advisable. Meticulous documentation of adverse events and treatment failures is crucial. Patient self-assessment and clinical scores are often biased but focussed on the basis of medical efforts: the well-being of the patient. Second-look arthroscopies produce fewer facts for quality control than expected but enable therapeutical intervention. Magnetic resonance imaging will be essential for cartilage assessment in the future. To date, the evaluation of tissue quality is experimental. Histology and immunohistochemistry are widely accepted as precise tools to characterize cartilaginous tissue. Ethical reasons prohibit daily use. Quality control following the repair of cartilage defects is complicated, expensive, and of variable outcome, but dangerous if neglected. Multiple insignificant results can lead to a sharp image of the postoperative condition and may enable quality control of treatment and surgery.
    Notes: Die meisten Verfahren zur Behandlung von Gelenkknorpeldefekten werden angewendet, ohne dass ihre Qualität zweifelsfrei nachgewiesen ist. Verschiedene Möglichkeiten der Qualitätssicherung können derzeit mit vertretbarem Aufwand routinemäßig eingesetzt werden. Die Beurteilung der Sicherheit einer Behandlung hinsichtlich Komplikationen und Therapieversagern ist von eminenter Bedeutung. Patientenfragebögen und klinische Scores sind subjektiv, orientieren sich aber am eigentlichen Ziel einer Therapie: der Wiederherstellung des Wohlbefindens des Patienten. Noch in den Anfängen, aber mit hervorragenden Perspektiven für die Zukunft steht die Magnetresonanztomographie. Knorpelqualität und -aktivität können heute noch nicht beurteilt werden. Die Kontrollarthroskopie nach der Behandlung von Gelenkknorpeldefekten liefert weniger harte Daten für die Qualitätssicherung als erwünscht, ermöglicht aber therapeutische Maßnahmen. Histologische Untersuchungen stehen im Ruf der unbestechlichen Präzision. Dem breiten Einsatz stehen jedoch fehlende Standards und berechtigte ethische Bedenken entgegen. Qualitätssicherung nach der operativen Behandlung von Gelenkknorpeldefekten ist schwierig, teuer und häufig ungenau – keine Qualitätssicherung ist oft gefährlich. Aus vielen, isoliert gesehen ungenauen Befunden werden die Bewertung eines Zustands immer sicherer und die Beurteilung der Qualität einer Behandlung möglich.
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  • 113
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    Cancer and metastasis reviews 19 (2000), S. 39-43 
    ISSN: 1573-7233
    Keywords: angiogenesis ; MRI ; permeability ; in vivo imaging ; hypoxia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Magnetic resonance imaging (MRI) provides a range of non-invasive measures for visualization of tumor angiogenesis in the clinic as well as in experimental tumor models. MRI methods were developed for assessment of spatial and temporal changes in perfusion, blood volume fraction, vascular permeability, vascular function, vascular maturation, vessel diameter and tortuosity. Molecular targeted contrast agents were used for mapping specific markers of neovasculature. These approaches were applied for analysis of a number of regulatory mechanisms controlling tumor angiogenesis and for preclinical evaluation of tumor response to antiangiogenic agents.
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  • 114
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    Journal of neural transmission 107 (2000), S. 1427-1436 
    ISSN: 1435-1463
    Keywords: Keywords: Brain ; MRI ; PSP ; MSA ; parkinsonism.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary. To establish diagnostic magnetic resonance imaging (MRI) criteria for differentiating progressive supranuclear palsy (PSP) from multiple system atrophy (MSA), magnetic resonance images from eight patients with probable PSP, 30 with probable MSA {nine striatonigral degeneration (MSA-P) and 21 olivopontocerebellar atrophy (MSA-C)}, and ten age-matched controls were retrospectively studied. Anteroposterior diameters in the midline sagittal T1-weighted image of the rostral (RMT) and caudal midbrain tegmentum (CMT), caudal pons and medulla were measured. Divergence of the red nuclei (RN) in the axial T2-weighted image was judged. All PSP images had a smaller RMT diameter than the lower limit of the normal range, showed RN divergence, and had a pontine diameter within the normal range. All MSA images had a CMT diameter within the normal range; no MSA images showed divergence of RN. Forty-four percent (4/9) of MSA-P and 76% (16/21) of MSA-C images had a pontine diameter smaller than the lower limit of the normal range. On basis of the results, we propose MRI diagnostic criteria for differentiating PSP from MSA.
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  • 115
    ISSN: 1436-2023
    Keywords: Key words Osteonecrosis ; Femoral head ; Bone marrow edema ; MRI ; Histology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Sequential magnetic resonance imaging (MRI) was performed on a 38-year-old woman with systemic lupus erythematosus who had received corticosteroid and had developed non-traumatic osteonecrosis of the femoral head. The initial MR finding was a band lesion on the T1-weighted image, which had been present before the onset of symptoms. At the onset of symptoms, a diffuse bone marrow edema pattern, with a low signal intensity on T1 and high signal intensity on T2-weighted images, was noted around the band lesion, extending to the femoral neck. Histopathologically, this region was found to consist of serous exudate, focal interstitial hemorrhage, and mild fibrosis, without any evidence of extension of osteonecrosis. It should be noted that extension of a low signal intensity area on MRI after the onset of hip pain may not be the result of the extension of osteonecrosis, but may represent concomitant edema due to collapse.
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  • 116
    ISSN: 1573-6792
    Keywords: EEG ; MRI ; Co-registration ; Spline ; Source localization ; Head model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Two classes of functional neuroimaging methods exist: hemodynamic techniques such as PET and fMRI, and electromagnetic techniques such as EEG/ERP and MEG. In order to fusion these images with anatomical information, co-registration with volumetric MRI is needed. While such co-registration techniques are well established for hemodynamic images, additional steps are needed for electromagnetic recordings, because the activity is only recorded on the scalp surface and inverse solutions based on specific head models have to be used to estimate the 3-dimensional current distribution. To date most of the experimental and clinical studies use multi-shell concentric sphere models of the head, solve the inverse problem on this simplistic model, and then co-register the solution with the MRI using homogeneous transform operations. Contrary to this standard method, we here propose to map the MRI to the spherical system by defining transformation operations that transform the MRI to a best-fitting sphere. Once done so, the solution points are defined in the cerebral tissue of this deformed MRI and the lead field for the distributed linear inverse solutions is calculated for this solution space. The method, that we call SMAC (Spherical Model with Anatomical Constrains) is tested with simulations, as well as with the following real data: 1) estimation of the sources of visual evoked potentials to unilateral stimulation from data averaged over subjects, and 2) localization of interictal discharges of two epileptic patients, one with a temporal, the other with an occipital focus, both confirmed by seizure freedom after resection of the epileptogenic region.
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  • 117
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    Neurological sciences 21 (2000), S. 53-55 
    ISSN: 1590-3478
    Keywords: Key words Genetic Creutzfeldt-Jakob disease ; Deafness ; MRI ; 14-3-3 protein
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We describe a case of genetic Creutzfeldt-Jakob disease (CJD) with deafness at the onset. We report clinical features, 14-3-3 protein positivity, electroencephalography and brain stem auditory evoked potential abnormalities, and high signal on magnetic resonance imaging in basal ganglia and temporal cortex. Similarities with CJD Heidenhain variant are discussed.
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  • 118
    ISSN: 1590-9999
    Keywords: Key words Disc herniation ; Lumbar spine ; Migration ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The majority of symptomatic lumbar disc herniations are located in a posterolateral position with resultant nerve root compression. Although caudal, rostral and lateral migrations of disc fragments are common, posterior epidural migration of an extruded free fragment from a lumbar disc herniation is a rare occurrence and sometimes may cause a dural sac compression with cauda equina syndrome. This retrospective case report describes a 63-year-old man with intractable lower back pain and cauda equina syndrome. Emergency magnetic resonance imaging (MRI) revealed a posterior epidural soft tissue compressing the dural sac. The lesion was hypointense on T1-weighted images, hyperintense on T2-weighted images and showed rim enhancement after intravenous injection of gadolinium. A laminectomy at L3 was performed and the extruded disc fragment was removed with dural sac decompression. Postoperatively the patient's radicular symptoms completely resolved. At the 2-year follow-up visit, the patient had recovered full motor, sensory and urinary functions. MRI is the modality of choice in the evaluation of an extruded free disc fragment and a cauda equina compression. In such cases a wide decompressive laminectomy is recommended.
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  • 119
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    Neurological sciences 21 (2000), S. 151-155 
    ISSN: 1590-3478
    Keywords: Key words Epilepsy ; Venous angioma ; MRI ; Vascular malformations ; Focal cortical dysplasia
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The purpose of this study was to evaluate the frequency and characteristics of epilepsy associated with cerebral venous angiomas (VA). We examined epileptic patients in which magnetic resonance imaging (MRI) showed VA. The characteristics of epilepsy and its relationships to VA were studied. Out of 1020 epileptic patients submitted to MRI in a 10-year period, 4 presented with VA. All had partial seizures, most frequently complex partial, with secondary generalizations in 3. Drug resistance was observed in 2. One patient had a small area of cortical dysplasia near the VA; another had a cutaneous angioma. In 2 patients, there was no topographic concordance between the VA and the focus on electroencephalography. Our study reveals that VA are rarely found in epileptic patients, differently from other vascular malformations, in particular cavernomas. Topographic and/or etiological relationships between VA and epilepsy are still undefined.
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  • 120
    ISSN: 1573-3297
    Keywords: Extended twin study ; methodology ; structural equation modeling ; intermediate phenotype ; MRI
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Psychology
    Notes: Abstract The hunt for genes influencing behavior may be aided by the study of intermediate phenotypes for several reasons. First, intermediate phenotypes may be influenced by only a few genes, which facilitates their detection. Second, many intermediate phenotypes can be measured on a continuous quantitative scale and thus can be assessed in affected and unaffected individuals. Continuous measures increase the statistical power to detect genetic effects (Neale et al., 1994), and allow studies to be designed to collect data from informative subjects such as extreme concordant or discordant pairs. Intermediate phenotypes for discrete traits, such as psychiatric disorders, can be neurotransmitter levels, brain function, or structure. In this paper we conduct a multivariate analysis of data from 111 twin pairs and 34 additional siblings on cerebellar volume, intracranial space, and body height. The analysis is carried out on the raw data and specifies a model for the mean and the covariance structure. Results suggest that cerebellar volume and intracranial space vary with age and sex. Brain volumes tend to decrease slightly with age, and males generally have a larger brain volume than females. The remaining phenotypic variance of cerebellar volume is largely genetic (88%). These genetic factors partly overlap with the genetic factors that explain variance in intracranial space and body height. The applied method is presented as a general approach for the analysis of intermediate phenotypes in which the effects of correlated variables on the observed scores are modeled through multivariate analysis.
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  • 121
    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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  • 122
    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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  • 123
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    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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  • 124
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    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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  • 125
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    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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  • 126
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    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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  • 127
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    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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  • 128
    ISSN: 1434-193X
    Keywords: Tetrakis(dimethylamino)naphthalenes ; Basicity ; Hydrogen bonds ; Cyclicvoltammetry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---For comparison to the recently described 2,3,6,7-tetrakis(dimethylamino)naphthalene (1) the three isomers 2,3, and 4 were synthesized. The basicities of this group of isomers are strongly dependent upon the different mutual orientations of the pairs of dimethylamino substituents: only the isomers 3 and, partially, 4, both with dimethylamino groups in adjacent peri-positions of the naphthalene, are strong “proton sponges”. For the isomers 1 and 2 with the same number and kind of twofold dimethylamino substituents in neighbouring ortho-positions, however, no significant basicity increase is observed. To explain this difference between the two groups of isomers it is suggested that in the ortho-pairs of 1 and 2 the C-N bonds diverge considerably, leading to an increased N···N distance and consequently to less stable [N···H···N]+ hydrogen bonds in contrast to the parallel C-N bonds in the peri-substituted isomers 3 and 4. X-ray crystal structure analyses of the bases and of some of the salts derived therefrom were solved and are discussed. Cyclic voltammetry indicates that 1 to 4 are strong electron donors, reacting easily to radical cations or dications which with suitable acids have been obtained as salts.
    Additional Material: 3 Ill.
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  • 129
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    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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  • 130
    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.
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  • 131
    ISSN: 1434-193X
    Keywords: Conjugation ; Boron ; Sensors ; Cyclic voltammetry ; Polymers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---New electropolymerizable aromatic compounds (i.e. pyrrole, thiophene, aniline) bearing boronic acid and ester substituents have been synthesized and their electrochemical behavior has been investigated. Functionalized polythiophene and polypyrrole films could be anodically generated in acetonitrile, whereas the polyaniline derivative was electroformed in an acidic aqueous solution. The electrochemical responses of some of these materials were changed when fluoride ions were added to the electrolytic solutions. The strongest modifications, caused by binding of fluoride by the immobilized boron, were observed for the polypyrrole derivative in hydroorganic media.
    Additional Material: 5 Ill.
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  • 132
    ISSN: 1434-193X
    Keywords: Heterocycles ; Zinc ; Palladium ; Catalysts ; Sulfur ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Organozinc halides derived from Grignard reagents behave differently in their reaction with ethyl (±±)-(2RS,3SR)-tetrahydro-4-methylene-2-phenyl-3-(phenylsulfonyl)furan-3-carboxylate (3) according to the hybridisation of the carbon ligand. During the development of short multi-component reactions for the synthesis of diverse functionalized ethyl 2,5-dihydrofuran-3-carboxylates it was discovered that aryl and vinyl zinc halides undergo clean reaction with 3 in the presence of Pd(PPh3)4. In contrast, when alkyl zinc halides are reacted with 3 in the presence of Pd(PPh3)4, reductive desulfonation of 3 is observed. Remarkably, in the absence of a transition metal catalyst, the allylic substitution of 3 with alkyl zinc halides proceeds cleanly and in moderate to good yield.
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  • 133
    ISSN: 1434-193X
    Keywords: Self-assembly ; Vapor-pressure osmometry ; Resorcin[4]arenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Resorcin[4]arene tetracarboxylic acids 5,6 (A) and resorcin[4]arene tetrapyridines 2,3 (P) self-assemble in chloroform solution to form stable heterotopic AP dimers. Data from NMR titration and dilution experiments, as well as from vapor-pressure osmometry (VPO), indicate that the AP dimer is formed with an association constant greater than 107 M-1. Solid-solution extraction experiments are indicative of the formation of a 2:1 trimer (A2P), while self-associated homotopic species (A2 and A3) can be detected by NMR and VPO. Analysis of the heterotopic noncovalent assembly process over a range of compositions shows that these other species are much less stable than the AP heterodimer, which is the exclusive species at an A/P concentration ratio of 1:1 (〉 99.7% of the total at 10 mM).
    Additional Material: 6 Ill.
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  • 134
    ISSN: 1434-193X
    Keywords: Sulfoxides ; β-Amino sulfones ; Mannich type reaction ; Lithium perchlorate ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The LiClO4-mediated one-pot reaction of aldehydes with (trimethylsilyl)dialkyl amines and the lithium salt of sulfoxides or sulfones, affords the corresponding β-(dialkylamino) sulfoxides and β-(dialkylamino) sulfones in high yields. The aminosulfoxidation reaction of aliphatic or aromatic aldehydes lacks diastereoselectivity, but the diastereomeric sulfoxides can be separated by HPLC or column chromatography for further use.
    Additional Material: 1 Ill.
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  • 135
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1741-1744 
    ISSN: 1434-193X
    Keywords: Bridged pyranose derivatives ; Ring enlargement ; Carbenes ; Glycosides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Addition of dichlorocarbene to the glycal (±±)-2 followed by cyclopropyl-allyl rearrangement leads to the chloro-2H-pyran (±±)-4. Oxidation of (±±)-4 and reduction of the obtained hydroxypyranone (±±)-5 gave the methyl pyranoside (±±)-6. The relative configuration of (±±)-6 was established by X-ray structural analysis of the corresponding acetate (±±)-7. The synthesis of the optically active starting materials (+)-2 and (-)-2 is also reported.
    Additional Material: 1 Ill.
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  • 136
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1745-1758 
    ISSN: 1434-193X
    Keywords: CMP-Neu5Ac analogues ; Enzyme inhibitors ; Substrate analogues ; Transition state analogues ; Transferases ; Carbohydrates ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Quinic acid was transformed into phosphitamides 16, 25, and 36, which could be readily linked to 5′-O-unprotected cytidine derivative 17. Ensuing oxidation of the obtained phosphite triesters with tBuO2H and hydrogenolytic de-O-benzylation furnished the corresponding phosphate diesters 18, 26, and 38. Base catalyzed removal of acetyl protecting groups, and methyl ester hydrolysis furnished CMP-Neu5Ac analogues 1d, 1e, and 2. Quinic acid was also transformed into 1,2-unsaturated diallyl α-hydroxymethyl-phosphate derivatives (R)- and (S)-46, which on reaction with cytidine phosphitamide 47 afforded the phosphite triesters. Subsequent oxidation with tBuO2H and then treatment with NEt3 gave phosphate diester derivatives (R)- and (S)-48. Deallylation, acetyl group removal, and methyl ester hydrolysis furnished (R)- and (S)-3, respectively. Treatment of (R)- and (S)-48 with DBU as a base led to acetic acid elimination, thus yielding, after de-O-allylation, acetyl group cleavage, and ester hydrolysis, diene derivative (E)-4. Donor substrate analogues 1d and 1e exhibited good α(2-6)-sialyltransferase inhibition (Ki: 2.0·10-4 and 2.0·10-5 M). However, transition state analogues (R)-, and particularly (S)-3 showed excellent inhibition properties (Ki: 1.6·10-6 and 2.7·10-7 M).
    Additional Material: 1 Tab.
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  • 137
    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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  • 138
    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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  • 139
    ISSN: 1434-193X
    Keywords: Cycloadditions ; Carbenes ; Nitrones ; Nitrilimines ; Pyrazolines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The reaction of tert-butylalkynyl chromium Fischer carbene complex 1 with nitrones 2 affords β-enamino-ketoaldehydes 4 by the light-promoted rearrangement of the corresponding [3+2] cycloadduct carbene complexes 3. On the other hand, [3+2] cycloaddition of chiral nonracemic Fischer alkenyl carbene complexes 19 with nitrilimines 10 yields enantiomerically pure Δ2-pyrazolines with high regio- and diastereoselectivity.
    Additional Material: 3 Ill.
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  • 140
    ISSN: 1434-193X
    Keywords: Asymmetric synthesis ; Zinc ; Transition structures ; QM/MM computations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Trimethylsilyl substitutions of the fenchyl alcohols [(1R,2R,4S)-exo-(2-Ar)-1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol, Ar = 2-methoxyphenyl (1) and Ar = 2-(dimethylaminomethyl)phenyl (2)] yield the chiral ligands 3 [Ar = 2-methoxy-3-(trimethylsilyl)phenyl] and 4 [Ar = 2-(dimethylaminomethyl)3-(trimethylsilyl)phenyl]. Increased reactivities and enantioselectivities in diethylzinc additions to benzaldehyde are obtained from 3 (63% ee R) and 4 (93% ee S), relative to 1 (26% ee S) and 2 (73% ee S). X-ray crystal structures of 3 and of its methylzinc complex 3-Zn reveal out-of-plane bending of the methoxy groups as major geometrical consequences of the trimethylsilyl substitutions. Analyses of QM/MM ONIOM μ-O transition-structure models for 1, 2, 3, and 4 show that trimethylsilyl-induced distortions of methoxy and of dimethylaminomethyl groups explain the observed increased enantioselectivities.
    Additional Material: 10 Ill.
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  • 141
    ISSN: 1434-193X
    Keywords: Palladium ; exo-π-Allylpalladium complexes ; Allylic alkylation ; Spiro compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The palladium(0)-catalyzed alkylation of 2,3-bis(acetoxymethyl)bicyclo[2.2.1]hepta-2,5-diene 1 with malonate-type enolates as nucleophiles is investigated. A monoalkylated product is formed first, and undergoes (depending on the nucleophile used) a second intramolecular reaction leading to spirocyclopropane-annulated bicyclo[2.2.1]heptene derivatives 5. The formation of endo spirobicyclic cyclopropanes adducts as major isomer is rationalized by assuming formation of an intermediate exo-(π-allyl)palladium complex.
    Additional Material: 2 Ill.
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  • 142
    ISSN: 1434-193X
    Keywords: Ketones ; Reductions ; Micelles ; Cobalt ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Operationally simple and environmentally benign procedures have been developed to selectively reduce different α,β-unsaturated ketones, 4,4-dimethylcyclohex-2-ene-1-one (1), isophorone (2), benzylideneacetone (3), chalcone (4) by NaBH4 or by the system NaBH4 + CoCl2. Alternative reaction media to the extensively used MeOH have been explored, and new procedures take advantage of the acceleration and chemoselectivity induced by water or by aqueous micellar solutions. It was possible to selectively and quantitatively afford pure products of 1,2 and of 1,4 reduction as well as the totally reduced compounds (yield and selectivity 〉 90%) by simple changes in the experimental conditions.
    Additional Material: 4 Ill.
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  • 143
    ISSN: 1434-193X
    Keywords: C-Glycosides ; Conformation analysis ; Molecular dynamics ; Selectins ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The conformational behavior of the C-glycosyl analogue of sialyl-α-(2→3)-galactose, synthesized as a glycosidase inhibitor, has been studied using a combination of NMR spectroscopy (J and NOE data) and molecular dynamics calculations. The obtained results show that the population distribution of conformers with respect to the orientation about the pseudo-glycosidic linkages is mainly controlled by steric interactions. This is in contrast to findings made for O-glycosides. In these natural compounds, the conformational behavior about the glycosidic linkage Φ is mainly governed by the exo-anomeric effect.
    Additional Material: 5 Ill.
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  • 144
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1815-1820 
    ISSN: 1434-193X
    Keywords: Asymmetric synthesis ; Palladium-catalysed couplings ; Palladacycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Chiral C2-symmetric N-benzylazetidines have been conveniently prepared from optically pure anti-1,3-diols without loss of enantiomeric purity. N-Debenzylation led to the corresponding N-unsubstituted azetidines, which were then subjected to palladium-catalysed coupling reactions with aryl bromides to afford chiral N-arylazetidines. (R,R)-N-Benzyl-2,4-dimethylazetidine has been employed in the synthesis of a new cyclopalladated complex, which can be used, for instance, as a chiral recognition agent for phosphorus ligands.
    Additional Material: 1 Tab.
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  • 145
    ISSN: 1434-193X
    Keywords: Cyclizations ; Spiro compounds ; Nucleosides ; Isomerizations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Syntheses of the spiro nucleosides 2′-deoxyhydantocidin 3a and its 1′-epimer 3b are described. The newly developed route involves a Horner-Wadsworth-Emmons condensation of the phosphonate 16 with the erythrose derivative 15 affording a mixture of six isomers which was fully assigned by NMR spectroscopy. The mixture was directly converted into the final compounds in an efficient base-catalyzed cyclization reaction. A base-catalyzed interconversion between the two isomers was observed.
    Additional Material: 2 Ill.
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  • 146
    ISSN: 1434-193X
    Keywords: Benzodiazepines ; Heterocycles ; Azeto[1,2-a]-1,5-benzodiazepines ; Cyclizations ; Cycloadditions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The reaction of o-phenylenediamine (4) with one, two or three equivalents of p-substituted 3-dimethylaminopropiophenone hydrochlorides 5a-e was studied. 4-Aryl-2,3-dihydro-1H-1,5-benzodiazepine derivatives 6a-e were obtained in good yields, along with the 1:2-adducts 7c-e and the unexpected 1:3-adducts rac-8c-e. The type of adduct formed is determined by the molar ratio of the reactants 4 and 5 and by the nature of the substituent in the para position of the propiophenone 5.
    Additional Material: 1 Ill.
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  • 147
    ISSN: 1434-193X
    Keywords: Cup-shaped PAHs ; Host-guest compounds ; Host-guest chemistry ; Cyclizations ; Semiempirical calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Cyclotrimerisation of benzo-polycyclic bromostannylalkenes 8a-d with Cu(NO3)2·3H2O in THF affords benzotri(benzonorbornadienes) 3a-d as a mixture of the syn and anti isomers. The ratio of syn to anti is close to the 1:3 statistical value in most cases (i.e. in cyclotrimers 3a,b,d), but highly in favour of the anti isomer in 3c, where steric hindrance by the methoxy groups plays an important role in the stereochemistry of the cyclotrimerisation. The substrates for the cyclotrimerisation, i.e. the bromostannyl alkenes 8a-d, were prepared from bromoalkenes 7a-d by treatment with base (LDA) and quenching with trimethyltin chloride. In turn, bromoalkenes 7a-d were prepared from alkenes 5a-d by radical bromination-elimination. The reaction conditions used were designed to minimise Wagner-Meerwein rearrangements that would lead to unwanted bromo isomers. The cup-shaped syn cyclotrimers 3a-d exhibit high electron density within the cavity as determined by AM1 semiempirical calculations of their electrostatic potential surfaces and are valuable substrates for supramolecular chemistry. As an example, it is shown that fullerene C60 is drawn into solution in acetonitrile by complexation with both the syn and anti trimer of benzonorbornadiene 3a.
    Additional Material: 1 Tab.
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  • 148
    ISSN: 1434-193X
    Keywords: Carbene complexes ; Enamines ; Metallatrienes ; Cyclopentadienes ; Dihydropyrroles ; spiro-Tetrahydropyrroles ; Iminium carbonylmetalates ; Dimetallapolyenes ; Tungsten ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Reactions of the [(1-alkynyl)carbene]tungsten complex (CO)5W=C(OEt)C≡CPh (1) with 1-aminocyclohexenes 2a-c and 7a-c afford different types of products depending on the amino substituents and the reaction conditions. (4-Aminocyclobutenyl)carbene complexes B have been shown to be generated in the first reaction step through a [2+2] cycloaddition. These are key intermediates and afford cross-conjugated tungstatrienes E, (conjugated) 1-tungsta-1,3,5-hexatrienes G, or (non-conjugated) 1-tungsta-1,3,6-heptatrienes F by following competing reaction pathways. Cross-conjugated 1-tungstatrienes 3 have been isolated in 52-74% yield by performing the reactions of 1-aminobenzocyclohexenes 2a-c with compound 1 in pentane. In dichloromethane instead of pentane, (conjugated) 1-tungsta-1,3,5-hexatrienes 4 are obtained, which subse-quently undergo fragmentation to give cyclopentadienes 6 (by π-cyclization) and dihydropyrroles (by α-cyclization) in a molar ratio dependent on the nature of the amino substituents. (Non-conjugated) 1-tungsta-1,3,6-heptatrienes 10 are generated upon reaction of 1-aminocyclohexenes 7a-c with compounds 1, which are transformed into cyclopentadienes 12 via conjugated 1-tungsta-1,3,5-hexatrienes 9 as intermediates. Reactions of 1-tungsta-1,3,6-heptatrienes 10 with the (1-alkynyl)carbene complex 1 afford dinuclear compounds 14, which subsequently yield indenes 15 (by two successive π-cyclization steps) and spiro-tetrahydropyrroles 16 (by both a π-cyclization and an α-cyclization step), depending on the steric bulk of the amino substituent.
    Additional Material: 3 Ill.
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  • 149
    ISSN: 1434-193X
    Keywords: Allyl alcohols ; Organocerium reagents ; Alkenes ; Addition reactions ; Cerium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Alkylcerium reagents add to the multiple bonds of allyl and propargyl alcohols in good yields and under mild conditions. The double bond can be reduced with lithium aluminum hydride in the presence of cerium trichloride. The regiochemistry of the attack depends on electronic factors.
    Additional Material: 1 Tab.
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  • 150
    ISSN: 1434-193X
    Keywords: Amidines ; Chiral bases ; N-Acyliminium ions ; Enantioselective catalysis ; Chiral pool ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The synthesis of four enantiopure hydroxyamidines is described. One amidine was obtained from (S)-pyroglutamic acid. Its key step involved the addition of phenylmagnesium bromide to the corresponding ester, affording the tertiary alcohol without detectable racemization. The second amidine was obtained by coupling of an (S)-malic acid derived N-acyliminium ion with β-naphthol. The other amidines were obtained from an (S)-serine-derived imide which was reduced to two diastereomeric lactams that were eventually transformed into the corresponding amidines.
    Additional Material: 1 Ill.
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  • 151
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 155-163 
    ISSN: 1434-193X
    Keywords: Macrocycles ; Cyclizations ; Strained compounds ; Ketophosphonate ; Iodoalkyne ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Two strategies have been explored to build the highly strained eleven-membered ring 2, a potential precursor for the biosynthetic key intermediate of the protoilludane family: an intramolecular Horner-Wadsworth-Emmons olefination and an intramolecular Nozaki-Hiyama-Kishi type-ring closure.
    Additional Material: 4 Tab.
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  • 152
    ISSN: 1434-193X
    Keywords: Neutral anion receptor ; Hydrogen bonds ; Urea moieties ; Donor-acceptor systems ; Macrocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The synthesis of macrocyclic and acyclic cleft-like anion receptors in which four hydrogen bond donating urea moieties are present in a preorganized fashion is described. NMR spectroscopy shows the complex formation with H2PO4- and Cl -. Cleft-like receptors bind H2PO4- in a 2:1 guest-host stoichiometry (Ka = 107M-2) in DMSO, whereas Cl - is bound in a 1:1 stoichiometry (Ka = 103M-1). The macrocyclic receptors form a 1:1 complex with H2PO4- (Ka = 103M-1 in DMSO) with a 100-fold selectivity for H2PO4- over Cl -.
    Additional Material: 3 Ill.
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  • 153
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 193-198 
    ISSN: 1434-193X
    Keywords: Nucleophilic substitutions ; Azulenes ; Hydroxylation ; Amination ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Hydroxylation of azulenes with tert-butylhydroperoxide proceeds efficiently at the 6-position when the former contain electron-withdrawing substituents in the five-membered ring. Similarly, VNS amination of azulenes proceeds with 4-amino-1,2,4-triazole; its anion, being an active nucleophile, also reacts with unsubstituted azulene. A variety of transformations of 6-hydroxyazulenes, such as substitution of the corresponding sulfonates with nitrogen, oxygen, sulfur, carbon nucleophiles and halogens, and the Claisen rearrangement of allylic ethers, is reported.
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  • 154
    ISSN: 1434-193X
    Keywords: Heterocycles ; Carbohydrates ; Imidazolidines ; Oxazolidines ; Spiro compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Prochiral 1,3-dihydroxyacetone forms racemic oxazolidine- and oxazoline-type spiro[4.4]nonanes upon reactions with potassium (thio)cyanate and cyanamide. In contrast, 1,3-diaminoacetone yields only the corresponding spiro-bisimidazolidinethione under similar conditions together with monocyclic by-products, but the spiro-bisimidazolidinone is accessible by reaction of 1,3-dichloroacetone with urea. The resolution of the racemic spiro-bisoxazolidinethione 2a was achieved by using brucine as the resolving agent.
    Additional Material: 1 Ill.
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  • 155
    ISSN: 1434-193X
    Keywords: Homogeneous catalysis ; Palladium ; Acetoxylation ; Acryloxylation ; Addition reactions ; Cyclooctadiene ; Cyclooct-4-enone ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Palladium-catalyzed acryloxylation of several cycloalkenes in the presence of the Pd(OAc)2/p-benzoquinone/MnO2 catalytic system is reported. This oxidation reaction yields allylic acrylates as the sole products through the intermediacy of an η3-allyl complex. However, with 1,5-cyclooctadiene (3), cyclooct-4-enone (4) is the major reaction product. Its formation results from oxidation, which is also observed in the palladium-catalyzed acetoxylation of 3. It has been shown that this is the result of a 1,2-trans addition (acryloxy-palladation), followed by a β-hydride elimination, which yields an enol acrylate or acetate. A second Markovnikov-oriented 1,2-trans-acryloxy-palladation on the latter yields a palladium complex, rearrangement of which gives 4.
    Additional Material: 1 Ill.
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  • 156
    ISSN: 1434-193X
    Keywords: Amino acids ; coupling ; N-Substituted amide ; Cyclizations ; Cyclic dipeptides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A short synthesis of new, functionalized seven-membered ring cyclic dipeptides is described. After the coupling of N-protected β-amino acids to N-substituted α-amino tert-butyl esters, the protective groups of the terminal functions were removed and the cyclization took place diastereoselectively in the presence of the coupling agent BOP. Amide substitution was found to be effective in promoting the cyclization of linear dipeptides.
    Additional Material: 1 Ill.
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  • 157
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 275-280 
    ISSN: 1434-193X
    Keywords: Radical reactions ; Substituent effects ; Nitrogen heterocycles ; Dihydropyridines ; Pyrrolines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A set of allene-tethered benzoyloximes (5) has been treated with nBu3SnH. Depending on their substitution pattern, a wide range of compounds has been obtained. If the stannyl radical adds on the allene, the C-centred radical thus formed undergoes either a 5-exo ring closure to give the cyclopentene derivatives 7 or a 6-endo ring closure onto the N atom to give the dihydropyridines 8. If the stannyl radical adds on the benzoyl moiety, an iminyl radical is formed which leads to the 3H-pyrroles 9 and the alkylidene-pyrrolines 10. Steric effects as well as polar effects are the factors governing the reaction course.Supporting information for this article is available on the WWW under //http://www.wiley-vch.de/contents/jc_2046/2000/99373_s.pdf or from the author.
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  • 158
    ISSN: 1434-193X
    Keywords: Antibiotics ; Configuration determination ; Heterocycles ; Hongoquercin A ; Terpenoids ; Total synthesis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---(±)-Hongoquercin A (1), the racemate of an antibacterial fungal metabolite, has been synthesized starting from geranylacetone (2) and ethyl orsellinate (ethyl 2,4-dihydroxy-6-methylbenzoate, 5). The structure (±)-1 has been confirmed by X-ray analysis of its ethyl ester (±)-10. Synthesis of the naturally occurring (+)-hongoquercin A from (-)-sclareol (11) established its configuration as depicted in 1.
    Additional Material: 1 Ill.
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  • 159
    ISSN: 1434-193X
    Keywords: Carbohydrates ; Amino sugars ; Protecting groups ; Glycosylations ; Trichloroacetimidates ; Oligosaccharides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The N-DMM-Protected lactosamine derivative 2 was readily transformed into the corresponding glycosyl donor 4 and into acceptor 5. A TMSOTf-catalyzed glycosidation afforded the derived tetrasaccharide 6 which led to glycosyl donor 9. Reaction of 9 with lactose derivative 10 as acceptor gave the desired hexasaccharide 11. Cleavage of all protective groups and N-acetylation afforded the target molecule 1b (lacto-N-neohexaose). Glycosylation of acceptor 10 with donor 4 furnished tetrasaccharide 16 which, employing standard procedures, gave acceptor 18. Glycosylation of 18 with donor 9 furnished, under standard conditions, octasaccharide 19. Cleavage of all protective groups and N-acetylation afforded the target molecule 1c (lacto-N-neooctaose). Both 1b and 1c were obtained in good overall yields.
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  • 160
    ISSN: 1434-193X
    Keywords: Sharpless asymmetric dihydroxylation ; Asimilobin ; Tetrahydrofuran ring ; Wittig reactions ; Annonaceous acetogenins ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The most efficient method for the synthesis of the trans/threo/trans-bis(tetrahydrofuran) (THF) ring unit was established, and the first total synthesis of (-)-asimilobin and its diastereomer was then accomplished in twelve and fourteen steps, respectively, from trans-1,5,9-decatriene, by a convergent route with a Wittig reaction as the key step. By virtue of these synthetic results, the absolute configuration of the bis(THF) unit in naturally occurring asimilobin should be corrected.
    Additional Material: 3 Ill.
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  • 161
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    Liebigs Annalen 2000 (2000), S. 381-385 
    ISSN: 1434-193X
    Keywords: Enynes ; Macrocycles ; Coordination chemistry ; Crown compounds ; Radicals ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The complex molecular structure and interesting activation mechanisms of naturally occurring enediynes have inspired the synthesis of a variety of simpler model systems to mimic their properties. While in most model compounds nucleophilic attack, isomerization or bioreduction are used to activate the unsaturated system for diradical cyclization, some attempts have been made to employ metal-ion coordination for this purpose. Significant enhancement of the thermal reactivity has been achieved by metal-ion induced conformational and electronic changes of suitably substituted enediynes, such as 1, 5, 6, 17 and 18. Enediyne activation by stoichiometric or catalytic formation of vinylidene complexes, such as 22, from terminal alkynes has also been investigated. This paper summarizes recent results pursuing the activation of enediyne diradical cyclization by metal ions.
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  • 162
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 419-423 
    ISSN: 1434-193X
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The first enantioselective synthesis of enantiomerically pure (-)-wine lactone, (-)-1a, a fragrance constituent of various white wines, and its epimer (+)-1b, was carried out. The key steps are allylic substitution of (±)-2-cyclohexen-1-yl acetate (2) with dimethylmalonate using palladium complexes of phosphanyldihydrooxazol L1 or of the phosphanylcarboxylic acid L2 as catalyst, subsequent decarboxylation, iodolactonization and elimination, furnishing enantiomerically pure bicyclic lactone (+)-7 in 47% overall yield. The diastereoselective introduction of methyl groups by SN2′-type substitution with an organocopper compound and by enolate alkylation gave lactone (-)-1a in 43% overall yield from (+)-7.
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  • 163
    ISSN: 1434-193X
    Keywords: Aplykurodins ; Marine steroids ; C-C coupling ; Cyclic peroxides ; Lactonization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---An approach to the synthesis of aplykurodins, ichthyotoxic marine lactones, is presented. The carbon framework was derived from vitamin D3 by conversion of the readily accessible allyl alcohol 13 to the protected Grundmann's hydroxy ketone 22 and subsequent introduction of the C2 side chain through a Pd0-promoted coupling. Highly stereoselective hetero Diels-Alder reaction with O21 produced the key intermediate peroxide 25. Functional group transformations, coupled with a series of chemo- and stereoselective reactions, finally resulted in the synthesis of the unnatural analogue 17,18-dihydro-3,9-di-epi-aplykurodinone B (6).
    Additional Material: 2 Ill.
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  • 164
    ISSN: 1434-193X
    Keywords: Zeolites ; Radical ions ; Ring opening ; Electron transfer ; Oxidations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Incorporation of trans-1,2-diphenylcyclopropane (1) and its 3,3-D2-isotopomer into the channels of a redox-active pentasil zeolite (Na-ZSM-5) resulted in the formation of exo,exo-1,3-diphenylallyl radical (2•) and its 2-D1 isotopomer, respectively. This conversion requires oxidation, ring opening, and deprotonation, in an unspecified sequence. The allyl radical 2• is also formed upon incorporation of trans-1,3-diphenylpropene (3). A comparison with the solution photochemistry, in the presence or absence of added base, shows the conversion of 1 into 2• to be a zeolite-specific reaction. Incorporation of arylcyclopropanes 9 (R = H, OCH3) into ZSM-5 generated trans-propenylbenzene radical cations 10•+ (R = H, OCH3); the 2,2-D2 isotopomer of 9 (R = OCH3) gave rise to three different isotopomers of 10•+ (R = OCH3).
    Additional Material: 2 Ill.
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  • 165
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    Liebigs Annalen 2000 (2000), S. 485-490 
    ISSN: 1434-193X
    Keywords: Calixarenes ; Tripodal cryptand ; Extraction abilities ; Cations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The tripodal calixcryptands have been one of the scarcely explored fields in calixarene chemistry due to the difficulties in their preparation. The strategy presented in this paper shows that novel tripodal calixcryptands can be conveniently prepared by directly treacing p-tert-butylcalix[n]arenes (n = 4, 6) with a multi-functional polypode reagent, e.g. 1,1,1-tris(tosyloxyethoxyethoxymethyl)propane or tetrakis(tosyloxyethoxyethoxymethyl)methane, under selected conditions. The first example of 1,2,4-tripodal calix[6]cryptands has been prepared. Novel calix[6]crown and doublecalix[4]arenes were co-prepared. The extraction abilities of these novel calixcryptands toward several alkali metal ions, ammonium and alkylammonium ions are presented.
    Additional Material: 4 Ill.
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  • 166
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    Liebigs Annalen 2000 (2000), S. 521-525 
    ISSN: 1434-193X
    Keywords: Allyl aryl sulfones ; Nitroarenes ; Condensation reaction ; Lewis acids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Allyl aryl sulfones 2 react with aryl nitrocompounds 1 in a DBU/MgCl2 system giving the 4-arylsulfonyl quinolines 3. Some mechanistic aspects of the reaction are discussed. Application of this reaction to the formal total synthesis of the natural product (-)Eupolauramine is described.
    Additional Material: 1 Tab.
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  • 167
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    Liebigs Annalen 2000 (2000), S. 527-538 
    ISSN: 1434-193X
    Keywords: Furans ; Pyrans ; Dihydropyran-2-ylidenes ; Ring closure ; Addition reaction ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---On treatment with base the pentynones 8a-f undergo anionic addition reactions of the resulting enolate species to the alkyne moiety and afford the 2,5-disubstituted furans 10a-f in yields ranging from 10-91%. The proposed mechanism involves the 2-methylene-dihydrofurans 11 as intermediates which tautomerize to yield the observed products. In the case of the α-picolyl derivative 8g both possible enolates 12 and 13 are formed which are subsequently transformed to the products 10g and 14g, respectively. Starting with the hexynones 9a-e an analogous reaction takes place with the formation of the pyran derivatives 15 and 16 in comparable yields. Under the same reaction conditions the n-butyl ketone 9f gives rise to two isomeric compounds, namely the 4H-pyran 16f and the cyclohexenone 17. This result is explained by assuming initial formation of two isomeric enolates which react either by O- or C-attack on the carbon-carbon triple bond.
    Additional Material: 5 Tab.
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  • 168
    ISSN: 1434-193X
    Keywords: Alkylations ; Deaminated AdoHcy ; Decarboxylated AdoHcy ; Mitsunobu reaction ; Nucleosides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---5′-Acetylthio-5′-deoxy-2′,3′-O-isopropylideneadenosine (8) was directly prepared from commercially available 2′,3′-O-isopropylideneadenosine (7) and thioacetic acid under Mitsunobu conditions in almost quantitative yield. In situ cleavage of the acetylthio function of 8 followed by coupling with different alkyl bromides proceeded with high yields. Deprotection of the obtained 5′-thionucleosides yielded the S-adenosyl-L-homocysteine analogues decarboxylated AdoHcy (11), deaminated AdoHcy (14) and 5′-[3-(cyano)propylthio]-5′-deoxyadenosine (16) in good overall yields. Direct deprotection of the thionucleoside 8 delivered 5′-thio-5′-deoxyadenosine (18) in excellent yield. In addition, binding constants of these AdoHcy analogues and the DNA methyltransferase M·HhaI were determined in a fluorescence assay.
    Additional Material: 1 Ill.
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  • 169
    ISSN: 1434-193X
    Keywords: Amino ketones ; Homogeneous catalysis ; Aziridination ; Copper ; Enols ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A series of acyclic and cyclic enol derivatives 1 has been transformed into the corresponding α-amino-functionalized ketones 2 by means of enantioselective catalytic aziridination with chiral Cu complexes, prepared in situ from [Cu(MeCN)4]PF6 and the optically active ligands 3, by using (N-tosylimino)iodobenzene (PhINTs) as a nitrogen source. The best enantioselectivities (ee values of up to 52%) have been achieved for the electronically deactivated enol acetate 1aδ, but the incorporation of steric bulk and the substitution pattern at the enol double bond do not improve the ee values. The cyclic substrates react considerably less readily (only up to 45% conversion) compared to their acyclic counterparts (complete consumption). A transition structure is suggested for the asymmetric Cu-catalyzed aziridination of the enol acetate 1aδ in the presence of the chiral ligand 3b that could account for the sense of the (R)-configured product 2a.
    Additional Material: 1 Ill.
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  • 170
    ISSN: 1434-193X
    Keywords: Porphyrins ; Chiral auxiliaries ; Macrocycles ; Pyrethroids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Esters, N,N-disubstituted amides, and a N-acylurea derived from the enantiopure industrial intermediate (1R)-cis-hemicaronaldehydic acid (or biocartol) are convenient synthons for the preparation of a series of chiroporphyrins by condensation with pyrrole. These chiral meso-tetracyclopropylporphyrins are obtained exclusively as the D2-symmetric α,β,α,β atropisomer, generally in low to moderate yields (2-20%), and in the urea case in excellent yield (60%). Hydrolysis of the urea substituents affords a chiroporphyrin with mono-N-substituted amide groups. 1H-NMR spectroscopy indicates that the ester, amide, and urea stereogenic groups sit on the porphyrin close to the metal binding site and restrict substrate or ligand access along a C2-symmetric groove. This structural feature of chiroporphyrins and of their metal complexes is of high potential interest in asymmetric catalysis and chiral recognition.
    Additional Material: 3 Ill.
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  • 171
    ISSN: 1434-193X
    Keywords: Cyclophanes ; Molecular recognition ; Molecular shuttles ; Rotaxanes ; Template-directed synthesis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Two dumbbell-shaped compounds (8 and 11), each composed of two polyether chains intercepted by a 1,4-dioxybenzene recognition site, terminated by tetraarylmethane-based stoppers, and emanating from a central 9,10- or a 2,6-dioxyanthracene unit, have been synthesized. Two [2]rotaxanes (9 · 4 PF6 and 12 · 4 PF6) have been prepared by interlocking these dumbbell-shaped compounds (8 and 11) with a bipyridinium-based tetracationic cyclophane (15 · 4 PF6) - namely, cyclobis(paraquat-p-phenylene). A [3]rotaxane (10 · 8 PF6) incorporating two cyclophane components (15 · 4 PF6) was also obtained when the 9,10-dioxyanthracene-containing dumbbell-shaped compound (8) incorporating two 1,4-dioxybenzene recognition sites was employed. The 1H-NMR spectroscopic investigation of the [2]rotaxanes (9 · 4 PF6 and 12 · 4PF6) revealed that the cyclophane component encircles one of the two 1,4-dioxybenzene recognition sites in the 9,10-dioxyanthracene-containing [2]rotaxane (9 · 4 PF6) and the 2,6-dioxyanthracene unit in the other [2]rotaxane (12 · 4 PF6). These structures have been confirmed by UV/Vis and electrochemical experiments. Comparison with the spectroscopic properties of simple model compounds shows the presence of electronic interactions which lead to (i) the occurrence of very efficient energy transfer processes in the dumbbell-shaped components and (ii) perturbations in the absorption spectra with appearance of two charge-transfer absorption bands and complete luminescence quenching in the [2]rotaxanes. For the 2,6-dioxyanthracene-containing [2]rotaxane (12 · 4 PF6), it has been demonstrated that the cyclophane can be displaced from the dioxyanthracene to the 1,4-dioxybenzene station upon electrochemical oxidation.
    Additional Material: 9 Ill.
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  • 172
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    Liebigs Annalen 2000 (2000), S. 627-631 
    ISSN: 1434-193X
    Keywords: Complex nucleoside ; Antibiotics ; Radicals ; Zn-Cu couple ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Homosinefungin 5, which can be considered as an analogue of S-adenosylmethionine (SAM) and of S-adenosylhomocysteine (SAH), has been synthesized by means of a sequence in which the key step was the addition of a radical, produced by the simple treatment of an iodide precursor with a zinc-copper couple, to suitably activated olefins.
    Additional Material: 1 Ill.
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  • 173
    ISSN: 1434-193X
    Keywords: Amide linkage ; Phosphodiester ; Hammerhead ribozyme ; Oligonucleotides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A nucleoside dimer in which the natural phosphodiester bond is replaced by an isosteric amide linkage has been prepared. This dimer analogue was subsequently incorporated chemically at the cleavage position of a hammerhead ribozyme substrate. Although the resulting substrate analogue exhibited a high affinity for the ribozyme as shown by gel retardation assays, the amide bond proved to be fully resistant to cleavage under standard conditions of ribozyme cleavage activity.
    Additional Material: 3 Ill.
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  • 174
    ISSN: 1434-193X
    Keywords: Solid-phase synthesis ; Wang resin ; Hetero Diels-Alder reactions ; Dihydropyrans ; Reductive reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The OH groups of Wang resin were esterified with benzylidenepyruvic acid (1) to give the immobilized 1-oxabutadiene 2. The latter reacted with vinyl ethers 3a-h (dienophiles) in the presence of Eu(fod)3, and the resulting adducts 4a-h underwent reductive cleavage with LiAlH4 to afford the dihydropyrans 5a-h in high (62 to 100%) overall yields. A similar sequence carried out under conventional homogeneous liquid phase conditions led to significantly lower yields. The endo/exo selectivity of the cycloaddition reaction was the same in both cases.
    Additional Material: 2 Tab.
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  • 175
    ISSN: 1434-193X
    Keywords: Cationic amphiphiles ; Transfection ; Pyridinium salts ; Vesicles ; Lipoplex ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Pyridinium amphiphiles have found practical use for the delivery of DNA into cells. Starting from 4-methylpyridine, a general synthesis has been devised for the production of pyridinium amphiphiles which allows variation in both the hydrophobic part and in the headgroup area of the compounds. By means of differential scanning microcalorimetry, zeta potential, particle size measurements and cryo electron microscopy, some characteristics of the pyridinium amphiphile/DNA complexes have been determined.
    Additional Material: 2 Ill.
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  • 176
    ISSN: 1434-193X
    Keywords: Pauson-Khand reaction ; Cyclopentenones ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---1-Methyl-norbornene ester 9 and 1-methyl-2,3-diazabicyclo[2.2.1]heptene ester 10 were employed in intermolecular Pauson-Khand reactions with various terminal alkynes 11a-f to give the dimethyl 1-methyltricyclo[5.2.1.05,9]dec-7-en-6-one 2,3-dicarboxylates 12 and 13, and diethyl 2,3-diaza-1-methyltricyclo[5.2.1.05,9]dec-7-en-6-one 2,3-dicarboxylates 14 and 15, respectively. Whereas the co-cyclization of norbornene 9 with alkynes 11 bearing small substituents R resulted in the preferred formation of 12 (12:13 ≤ 85:15), regioisomer 13 was obtained as the major product when sterically bulky alkynes were employed (12:13 ≥ 6:94). For 2-methyl-3-butyn-2-ol 11e a strong temperature dependency of the regioselectivity was found. The ratio of regioisomers (12e:13e) changed from 95:5 at -25 °C to 12:88 at 120 °C in toluene. In contrast, reactions with 2,3-diazanorbornene 10 showed only moderate regioselectivities in favour of 14 (14:15 ≤ 69:31), regardless of the temperature and the size of R. The observed regioselectivities support a mechanism for the Pauson-Khand reaction in which the apical rather than the basal anti oriented carbon monoxide ligand of cobalt alkyne complex 1 is replaced by the alkene.
    Additional Material: 1 Ill.
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  • 177
    ISSN: 1434-193X
    Keywords: Reverse-turn mimics ; γ-Turns ; β-Turns ; β-Hairpins ; Peptides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Conformational analysis of N-acetylated hexapeptide mimics incorporating a bicyclic lactam (1-4) was carried out by a combination of 1H-NMR spectroscopy, IR spectroscopy, and computer modeling. The nature of the bicyclic lactam determines the turn motifs and the folding patterns of these constrained peptides. The (5,6)-bicyclic lactam derivatives 1 and 2, characterized by a type-II' β-turn (C=O3···H6-N), are very compact intramolecularly H-bonded structures. The (5,7)-bicyclic lactam derivative 3, characterized by an inverse γ-turn (C=O4···H6-N), is a quite flexible “tweezer-like” structure.
    Additional Material: 4 Ill.
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  • 178
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    Liebigs Annalen 2000 (2000), S. 707-711 
    ISSN: 1434-193X
    Keywords: Radical reactions ; Photolysis ; X-ray scattering ; Rearrangements ; Semiempirical calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The previously reported tandem cyclisation of N-aryl α-(2-cyanophenyl)sulfanyl imidoyl radicals affords one quinoxaline derivative arising from exclusive 1,6-cyclisation of the final iminyl radical onto the N-aryl ring. When the imidoyl radicals are generated by addition of photolytically generated (2-cyanophenyl)sulfanyl radicals to isocyanides, the reaction also gives small amounts of a by-product that is formed by an analogous route and whose X-ray crystallographic data are reported here. The formation of this product entails a rare ortho-selective photo-Fries rearrangement of the starting disulfide, followed by addition to the isocyanide and regioselective 1,5-cyclisation of the resulting imidoyl onto only one of the two available radical acceptors, i.e. the cyano group and the sulfide moiety. Semiempirical MNDO-d calculations were performed in order to throw some light on the factors affecting these competitive cyclisations.
    Additional Material: 2 Ill.
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  • 179
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    Liebigs Annalen 2000 (2000), S. 713-721 
    ISSN: 1434-193X
    Keywords: Reductive alkylation ; Acenaphthylenes ; Carbanions ; Polycycles ; Single-electron transfer ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Reaction of the 5-hydroacenaphthylene anion with benzyl halides proceeds at carbon atom 1 as well as at carbon atom 2a, in the latter case creating a quaternary centre. The hardness-softness of the electrophiles was shown to play only a minor role in determining the regioselectivity of the reaction of the hydroanion with several benzyl and alkyl halides: the leaving group hardly affects the ratio of 1- and 2a-substituted products. This indicates that the alkylation might proceed by an electron transfer (SET) instead of an SN2 mechanism. Further evidence for SET was obtained by the use of free radical and electron scavengers. The substitution products 1-benzylacenaphthene and 2a-benzyl-2a,5-dihydroacenaphthylene could be isolated and purified.
    Additional Material: 3 Ill.
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  • 180
    ISSN: 1434-193X
    Keywords: Isotopic labeling ; Isotopic labeling ; Isotopic labeling ; Deuterium ; Carbon-13 ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Three selectively labeled propynes were prepared either with deuterium or carbon-13 at position 3 and doubly labeled with carbon-13 at positions 1 and 2 by an alkylation reaction from the corresponding labeled or unlabeled monolithio acetylides and dimethylsulfates. Their lithiation with nBuLi gave the corresponding propynyllithium derivatives which reacted with dimethyl squarate to afford the corresponding propargylic alcohols. These were thermolysed in p-xylene to furnish [5-D3-methyl]-, [5-13C-methyl]-, and [5,6-13C2-2,5-cyclohexadienyl]ubiquinone. The farnesyl side chain was introduced onto the labeled quinones with farnesyl trimethyltin under BF3 catalysis to provide [5-D3-methyl]-, [5-13C-methyl]-, and [5,6-13C2-2,5-cyclohexadienyl]ubiquinone 3 (6c, 6b, 6a, respectively).
    Additional Material: 1 Ill.
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  • 181
    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.
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  • 182
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    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.
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  • 183
    ISSN: 1434-193X
    Keywords: Bisdiazenes ; Homoconjugation ; Photochemistry ; Heterocycles ; Diazenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Rigid N=N/N=N (diazene/diazene) systems (F) consisting of more or less alkylated DBH and DBO chromophoric units (1, 2, X-ray structures), with very short π,π distances [d = 2.849 (1a, av.), 2.822 Å (2)] and almost perfect syn-periplanar π,π alignments [ω = 168.6 (1a), 174.2° (2)] as well as the more flexible, less “proximate” metathesis isomers (3a,c, 27a,c, d 〉4.6 Å, ω = 90-100°) have been synthesized. Homoconjugate π,π interaction (in 1, 2, not in 3, 27) is deduced from UV spectroscopic measurements [π → π* maxima at 239 (234) nm (sh, 260)], while PE analyses furnished only small interaction parameters (1a: 〈0.3 eV). The potential of the novel syn-periplanar N=N/N=N motif in 1 and 2 for the synthesis of somewhat exotic polyheterocycles has been explored by calculation (B3LYP) as well as experimentally: i.a. kinetically stabilized, all-cis-peralkylated tetrazolidines (38, 44) and perhydro-1,2,4,5-tetrazines (41, 47) have become accessible (i.a. via novel azomethine/diazene and azomethine/azomethine cycloadditions). In 1a with its unreactive DBO chromophoric subunits, in the “buttressed” derivatives 1b-d, as well as in the DBH/DBO combination 2, and likewise in more ‘distant’ 27 (differently from the analogous C=C/C=C and N=N/C=C systems), irrespective of the excitation conditions employed (light of λ ≥≥ 280, 254 nm, low temperature matrix irradiation, acetone sensitization) no [2+2]photocycloaddition was observed. Instead exclusively N2-elimination took place. It is argued that unproductive N=N/N=N photocycloaddition would have become observable through metathesis isomerization of the respective tetrazetidines.
    Additional Material: 9 Ill.
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  • 184
    ISSN: 1434-193X
    Keywords: Photochemistry ; Heterocycles ; Diazenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Of two very proximate syn-periplanar bisdiazenes (1,2) mono-, di-, tri- and tetra-N-oxides were prepared, representing six combinations of the individual N=N/N=NO/ON=NO chromophores. According to DFT calculations (B3LYP/6-31G*), [2+2]photocycloaddition to the respective oxidized tetrazetidines is significantly to moderately endothermic. The metathesis isomerization of the oxidized tetrazetidines is generally highly exothermic and kinetically increasingly favorable with increasing oxidation state. In practice, four out of the six bichromophoric combinations undergo selectively, in competition with N2 elimination from a DBH unit (13) still partially, metathesis isomerization upon π → π* excitation (monochromatic 254 nm light). In the case of the syn-N=NO/N=NO combinations (5/6, 14), the photoaddition is thermally reversed. For a ON=NO/N=N combination (30), internal electron transfer is responsible for a complex reaction pattern. The preparative value of the metathesis reactions, though, is limited: The metathesis-derived bis[diazene mono(di)oxides] undergo relatively fast secondary photoreactions, while the tri(tetra)oxides undergo rapid thermal transformations. For the N=N/N=NO systems (12), of three potential pathways for its metathesis isomerization, the one that takes place via σ-symmetric intermediates (63, 64) is excluded by virtue of the retention of optical purity in the photometathesis of a highly enriched enantiomer [(-)-12]. Matrix irradiation experiments (12 K, IR control) with 12 result in the appearance of a kinetically highly labile transient. Supported by DFT calculations it is concluded that in the metathesis reactions, the respective tetrazetidine oxides (increasingly destabilized by interactions between oxygen lone pairs and NNσ* orbitals) function as vibrationally excited transients. That thermal reversion of these transients might be a general, nonproductive competition, is suggested by the experimental verification of a “reversed photometathesis” (51 → 15) and by the generally low rates in product formation upon irradiation. The question remains to be answered why in structurally analogous molecular skeletons, [2+2]photocycloaddition occurs in the C=C/N=N and variously oxidized N=N/N=N, and not, however, in the parent N=N/N=N combinations.
    Additional Material: 4 Ill.
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  • 185
    ISSN: 1434-193X
    Keywords: Amphiphiles ; Ketone ; Glycosides ; Electron transfer ; Chiral resolution ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Electroreducible amphiphilic aromatic ketones derived from D-glucose and D-glucofuranurono-6,3-lactone (D-glucurone) have been synthesized by Schmidt condensation and reaction of the unprotected lactone with the appropriate substrates, respectively. The macroscale electrolyses of the glucose derivatives, performed in an aprotic solvent (DMF), yield the pinacols possessing two glycosidic side chains. Under the same conditions of electrolysis with the D-glucurone derivative, the glyosidic carbon-oxygen bond is cleaved. The use of a redox mediator (couple anthracene-•/anthracene) has demonstrated that a glucosidic bond can be reduced by a homogeneous electron transfer. In the presence of a proton donor the expected D-glucuronic pinacol is obtained. The radical-radical coupling involves the formation of two chiral centers. The diastereo- and the enantioselectivity of the reaction have been studied by 1H- and 2H-NMR spectroscopy, respectively.
    Additional Material: 6 Ill.
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  • 186
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 837-840 
    ISSN: 1434-193X
    Keywords: Chiral auxiliaries ; Analytical methods ; Through-space interactions ; Lactic acid ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The enantiomeric purity of a chiral compound is determined by NMR spectroscopic analysis of the diastereomers formed with a chiral derivatizing agent. Fluorinated O-aryllactic acids (FAC) 1 are efficient chiral reporters, whose spectacular remote anisotropic effects allow an easy identification and measurement of diastereomers. The remote effects are attributed to the particular design of FAC esters relative to other CDAs.
    Additional Material: 4 Ill.
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  • 187
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 849-855 
    ISSN: 1434-193X
    Keywords: Marine alkaloids ; Heterocycles ; Natural products ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Ascididemine (9H-quino[4,3,2-de][1,10]phenanthrolin-9-one) (1) and an isomer (9H-quino[4,3,2-de][1,7]phenanthrolin-9-one) (4) have been synthesized starting from 1,4-dimethoxyacridone (7). The acridone was converted into 1,4-dimethoxy-9-ethynylacridine (11) by a triflate coupling. The ethynylacridine was converted in one-pot into 3H-6-methoxypyrido[2,3,4-kl]acridine (15) by reaction with sodium diformylamide; the mechanism of this key transformation is discussed. Conversion into 6H-4-bromopyrido[2,3,4-kl]acridin-6-one (19) and 6H-pyrido[2,3,4-kl]acridin-6-one (17), followed by reaction of each of these under high pressure conditions with acrolein N,N-dimethylhydrazone, gave ascididemine and its isomer, respectively.
    Additional Material: 2 Ill.
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  • 188
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 861-866 
    ISSN: 1434-193X
    Keywords: DNA ; Dihydroxyacetone monophosphate ; Aldolase ; Carbon-13 ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A synthesis of [3′,4′-13C2]thymidine (1) is described in which [13C2]acetic acid (2) is converted into the nucleoside in twelve steps with 9% overall yield. D-2-Deoxyribose-5-phosphate aldolase (DERA, EC 4.1.2.4) and triosephosphate isomerase (TPI, EC 5.3.1.1) are used for the stereocontrolled formation of D-[3,4-13C2]-2-deoxyribose-5-phosphate (8) from [2,3-13C2]dihydroxyacetone monophosphate (DHAP, 7) and acetaldehyde in 80% yield. The route permits the introduction of isotopically enriched carbon atoms at any position or combination of positions in the furanose ring and the product can be coupled with any of the four naturally occurring base moieties.
    Additional Material: 1 Ill.
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  • 189
    ISSN: 1434-193X
    Keywords: Benzothiazole carbene ; Palladium complex ; Homogeneous catalysis ; C-C coupling ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The first diiodo palladium complex with nucleophilic benzothiazole carbenes as ligands has been synthesized and characterized. The complex, which is extraordinarily stable towards heat, oxygen, and moisture, has been found to show good catalytic activity in the Heck coupling reaction.
    Additional Material: 1 Ill.
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  • 190
    ISSN: 1434-193X
    Keywords: Asymmetric synthesis ; Addition reactions ; Sulfones ; Alkylations ; Amines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The aza-Michael addition of enantiopure 1-aminopyrrolidines to (E)-alkenyl sulfones in the presence of a catalytic amount of ytterbium trifluoromethanesulfonate [Yb(OTf)3] yields β-hydrazino sulfones in moderate to good yields and with diastereoselectivities of up to ≥ 98%. The latter undergo reductive N-N bond cleavage with BH3 · THF and, after N-protection with Boc2O or benzyl bromide, afford N-protected β-amino sulfones with moderate to high enantiomeric excesses (ee = 42 to ≥96%) without racemization. Subsequent α-alkylation of the N,N-dibenzyl protected β-amino sulfones with various electrophiles yields α-alkyl-β-amino sulfones in excellent yields (88-97%) with high diastereomeric (de ≥96 to ≥98%) and enantiomeric purity (ee = 94 to ≥96%). The absolute configuration of the new stereogenic centre was determined by X-ray structural analysis and confirmed by NMR spectroscopy (NOE experiments). Possible reaction mechanisms for the conjugate addition and α-alkylation are presented.
    Additional Material: 5 Ill.
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  • 191
    ISSN: 1434-193X
    Keywords: Dinitrothiophene ; Ring-opening ; Dinitrobutadienes ; Pyrrolidines ; Pyrroles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The reactions between 1,4-diaryl-2,3-dinitro-1,3-butadienes 1a-d and primary alkylamines gave high yields of N-alkyl-2,5-diaryl-3-alkylamino-4-nitropyrrolidines 2 as pure all-trans diastereomers via an unusually favoured 5-endo-trig ring closure. The stereochemistry of compounds 2 has been attributed through an X-ray crystal structure analysis of the acetyl derivative 5 of 2ai. Amine elimination from 2 gave the N-alkyl-2,5-diaryl-3-nitro-3-pyrrolines 3 which could be easily aromatized to the corresponding pyrroles 4.
    Additional Material: 1 Ill.
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  • 192
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    Liebigs Annalen 2000 (2000), S. 921-928 
    ISSN: 1434-193X
    Keywords: Gas-phase chemistry ; Phenoxy radicals ; Dioxins ; Phenoxyphenols ; Reaction mechanisms ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Phenols are demonstrated precursors of “dioxins” - polychlorinated dibenzo-p-dioxins (DDs) and dibenzofurans (DFs) - in thermal processes, especially incineration. Heterogeneous catalysis, depending on conditions, can play an important role, but mere gas-phase combination of phenolic entities to ultimately DD and/or DF is always possible. The present paper addresses the fundamental role of phenol itself. Phenol has long been known to give DF upon pyrolysis and in similar thermal reactions. In the liquid phase under oxidative conditions it yields five condensation products (A-E); this clearly occurs through the dimerization of two phenoxy (PhO) radicals, followed by enolisation/rearomatisation. Our study shows that in the gas phase, at the lower T end, such dimers are also formed, but still with very little DF. That DF, indeed, is almost the only condensation product at elevated temperatures is substantiated by thermochemical-kinetic analysis (favouring the pathway of ortho-C/ortho-C combination of two PhO radicals), as well as by results obtained with two plausible intermediates, viz. 2,2′-dihydroxybiphenyl (A) and 2-phenoxyphenol (C). Mechanisms for the requisite enolisation and dehydration steps leading to DF are discussed.
    Additional Material: 3 Ill.
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  • 193
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 939-946 
    ISSN: 1434-193X
    Keywords: Enediynes ; Vanadium ; C-C coupling ; Macrocycles ; Lactams ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A short synthesis of unfunctionalized lactenediyne 3 by closure of the ten-membered ring at the double bond site is reported. After failure of the known methodologies, this closure was eventually successfully achieved thanks to a highly stereoselective, vanadium(II)-mediated pinacol coupling of bis(alk-2-ynal) 7.Supporting information for this article is available on the WWW under //http://www.wiley-vch.de/contents/jc_2046/2000/99471_s.pdf or from the author.
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  • 194
    ISSN: 1434-193X
    Keywords: Leishmaniasis ; Pheromones ; Pheromones ; Terpenoids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Both the enantiomers of 9-methylgermacrene-B (1) were synthesized from the enantiomers of methyl 3-hydroxy-2-methylpropanoate (2). The male-produced sex pheromone of the sandfly Lutzomyia longipalpis (the vector of the protozoan parasite Leishmania chagasi) from Lapinha, Brazil, was identified as (S)-1 by GC comparison.
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  • 195
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 987-994 
    ISSN: 1434-193X
    Keywords: Addition reactions ; Octahydroacridine ; Polypyridines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A new octahydroacridine with a tert-butoxypropyl group in the 9-position was prepared and was used in the synthesis of new soluble annelated polypyridines. Quinquepyridine with 11 adjacent rings was prepared in 17-25% yield by condensation of an α-methylene ketone and an enolisable ketone in the presence of ammonium acetate under basic conditions.
    Additional Material: 4 Ill.
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  • 196
    ISSN: 1434-193X
    Keywords: Asymmetric hydroxylations ; Allyl ethers ; Carbohydrates ; Molecular modeling ; Molecular dynamics ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The catalytic asymmetric dihydroxylation of several allyl 2-O-benzyl-α-D-xylosides with AD-mix β and PYR(DHQD)2 shows almost no diastereofacial selectivity if the 3- and 4-OH groups are unprotected or acetylated. Acetal, benzyl ethers and benzoyl esters enhance the diastereoselectivity, in the opposite sense to that predicted by the “AD mnemonic”, which is completely lost using AD-mix α. In an attempt to understand this behaviour, computational studies of the asymmetric dihydroxylation (AD) of olefins using Sharpless' and Corey's catalysts have been carried out using molecular dynamics. A three-step algorithm was developed taking advantage of the enzyme-like behaviour of catalyst-olefin systems and applied using an ESFF force field. To validate our approach, the first sampling step procedure was then refined and performed using a modified CVFF force field. This led to a U-shaped model in good agreement with that proposed by Corey for the AD of allyl 4-methoxybenzoates, which brings to the fore a role for the methoxy group. This model also accounts for the observed enantioselectivity of styrene dihydroxylation. When applied to the AD of allyl xylosides using AD-mix β, our model accounts well for the observed diastereoselectivity. Both synthetic and modelling results confirmed that aromatic groups on the olefin could be involved in π-π stacking interactions with the aromatic rings of the catalyst and should be important, if not a prerequisite, to achieve high enantio- and diastereoselectivity.Supporting information for this article is available on the WWW under //http://www.wiley-vch.de/contents/jc_2046/2000/99372_s.pdf or from the author.
    Additional Material: 5 Ill.
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  • 197
    ISSN: 1434-193X
    Keywords: Oligonucleotides ; Conjugation ; Porphyrinoids ; Solid-phase synthesis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A convenient solid-phase synthesis of oligonucleotides conjugated at the 3′-end with a tetraphenylporphyrin residue, by means of a new polymeric support bearing as a linker a lysine derivative, has been developed. A porphyrin linked 17-mer, designed for antisense experiments, has been prepared in good yields, and its hybridization properties with a complementary DNA fragment evaluated by UV thermal analysis.
    Additional Material: 4 Ill.
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  • 198
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    Liebigs Annalen 2000 (2000), S. 1027-1036 
    ISSN: 1434-193X
    Keywords: Sterols ; Cyclopropene ; Vinylic bromides ; Vinylsilanes ; Dibromocyclopropanation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A synthesis of (23R)- and (23S)-23H-calysterols 2a and 2b from pregnanoic ester 10 is reported. Alkylation of 10 with dibromide 19b, followed by reduction of the carboethyloxy group to a methyl group, afforded (Z)-vinylic bromide 22. Dibromocyclopropanation of 22 yielded the diastereomeric tribromocyclopropane derivatives 15c and 15d. The corresponding 3-hydroxy-5-ene 17c was transformed into 2a via 25 and a cyclopropenyllithium intermediate. An alternative synthetic route involving vinylsilane 13 and (E)-vinylic bromide 14 has also been examined.
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  • 199
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1045-1050 
    ISSN: 1434-193X
    Keywords: Hydrolysis ; Nucleophilicity ; α-Effect ; Metal ion complexes ; Oximes ; Biomimetic models ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A kinetic study of the reactivity in the cleavage of p-nitrophenyl acetate of a series of 2-pyridineoximes, 1-4, and their complexes with NiII, ZnII and CuII is reported. Complexation of the oximic ligands leads to a remarkable increase in the acidity of the oximic group, following the order CuII 〉 NiII 〉 ZnII. The oximates of free ligands and their metal complexes, being α-nucleophiles, are quite effective in promoting the cleavage of PNPA. However, the reactivity, as defined by the second-order rate constants, is not predictably related to the acidity of the oximic function. The corresponding Brønsted plot shows a linear behaviour up to a pKa value of ca. 8, above which the reactivity of the uncomplexed oximic functions levels off to a limiting value. In the case of the metal ion complexes, a large effect of the ligand structure on the reactivity was observed. As a consequence, complexes of appropriate ligands and metal ions show a reactivity that exceeds the apparent limiting one of the oximates. The origin of such effects and their possible implications in the development of new reactivators of phosphorylated acetylcholinesterase are discussed.
    Additional Material: 1 Ill.
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  • 200
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1061-1063 
    ISSN: 1434-193X
    Keywords: Photochemistry ; Matrix isolation ; Density functional calculations ; Isomerizations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Ultraviolet irradiation of matrix-isolated formamide (1) in solid argon with light of wavelength 248 nm leads to the formation of formimidic acid (2). Comparison of the experimental IR spectrum of the photoproduct with the calculated IR spectrum of 2 shows clearly that two rotamers 2a and 2b are formed.Supporting information for this article is available on the WWW under //http://www.wiley-vch.de/contents/jc_2046/2000/99501_s.pdf or from the author.
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