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  • 1985-1989  (12)
  • 1
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hormaomycin, a Novel Peptide Lactone with Morphogenetic Activity on StreptomycesA culture identified as Streptomyces griseoflavus (strain W-384) has been found to produce a novel peptide-lactone antibiotic designated hormaomycin (6). The empirical molecular formula of the compound is established to be C55H69ClN10O14. The constituent amino acids of the antibiotic are suggested to be allothreonine (1; 1), isoleucine (2; 1), 3-methyl-phenylalanine (3; 2), and, for the first time identified from a natural source, 4-[(Z)-prop-1-enyl]-proline (4; 1) and 3-(2-nitrocyclopropyl)-alanine (5; 2). The amino acids were delivered by acidic hydrolysis and assigned by high-resolution- GC/MS analysis (after transformation to derivatives) in combination with extended 2D-NMR experiments of the antibiotic itself. From the latter, it became plausible that the N-terminus of the peptide chain is acylated by a Cl-containing derivative of 1H-pyrrol-2-carboxylic acid. Hormaomycin is active against some Gram-positive bacteria. In addition, the antibiotic exhibits potent aerial mycelium-inducing activity and effects the production of antibiotics.
    Notes: No abstract.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Conformational Analysis, XXV. - Conformations of Octasaccharide and Pentasaccharide Sequences in N-Glycoproteins of the Lactosamine TypeThe oligosaccharide sequences [β-D-Gal(1 → 4)β-D-GlcNAc(1 → 2)α-D-Man(1 → 3)]β-D-Gal-(1 → 4)β-D-GlcNAc(1 → 2)α-D-Man(1 → 6)β-D-Man(1 → 4)-D-GlcNAc (2), β-D-Gal(1 → 4)β-D-GlcNAc(1 → 2)α-D-Man(1 → 6)β-D-Man(1 → 4)-D-GlcNAc (3), β-D-Gal(1 → 4)β-D-GlcNAc(1 → 2)-α-D-Man(1 → 3)β-D-Man(1 → 4)-D-GlcNAc (4), and β-D-Gal(1 → 4)β-D-GlcNAc(1 → 2)α-D-Man-OMe (5), found in N-glycoproteins, were investigated by means of HSEA calculations with the program GESA to reveal the preferred solution conformations of these compounds. Experimental evidence of the calculated conformations was given by 1H and 13C NMR studies like NOE experiments, spin-lattice relaxation-time measurements and observation of special deshielding effects. NMR spectra analysis required application of 2-D-NMR techniques. As a conclusion of experimental and theoretical results the common sequences in the saccharides 2, 3, 4, and 5 exhibit very similar conformations. The pentasaccharide 4 takes up a linear conformation whereas 5 shows a bent arrangement of the pyranose rings (‚gt conformation‘) which results in a relatively close contact between the α-D-Man unit and the reducing D-GlcNAc unit. Analogously, both conformations, the linear and the bent one, occur in the octasaccharide 2.
    Notes: Die bevorzugten Konformationen der in N-Glycoproteinen vorkommenden Oligosaccharid-Sequenzen [β-D-Gal(1 → 4)β-D-GlcNAc(1 → 2)α-D-Man(1 → 3)] β-D-Gal(1 → 4)β-D-GlcNAc-(1 → 2)α-D-Man(1 → 6)β-D-Man(1 → 4)-D-GlcNAc (2), β-D-Gal(1 → 4)β-D-GlcNAc(1 → 2)α-D-Man(1 → 6)β-D-Man(1 → 4)-D-GlcNAc (3), β-D-Gal(1 → 4)β-D-GlcNAc(1 → 2)α-D-Man(1 → 3)-β-D-Man(1 → 4)-D-GlcNAc (4) und β-D-Gal(1 → 4)β-D-GlcNA(1 → 2)α-D-Man-OMe (5) wurden durch HSEA-Berechnungen mit dem Programm GESA bestimmt. Die Überprüfung der Rechnungen erfolgte durch 1H- und 13C-NMR-spektroskopische Experimente wie NOE-Untersuchungen, Spin-Gitter-Relaxationszeitmessungen und Beobachtung spezieller Abschirmungseffekte. Die Interpretation der NMR-Spektren erfolgte mit Hilfe von 2-D-NMR-Techniken. Die in 2, 3, 4, und 5 gemeinsam auftretenden Sequenzen haben alle sehr ähnliche bevorzugte Konformationen. Während 4 eine weitgehend gestreckte Konformation aufweist, zeigt 5 bevorzugt eine gebogene gt-Konformation, bei der die α-D-Man-Einheit der reduzierenden D-GlcNAc-Einheit nahe steht. Beide Formen kommen in 2 entsprechend vereint vor.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1985 (1985), S. 113-128 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Branched and Chain-extended Sugars, XXVIII.  -  Synthesis of 6-Amino-6-deoxyhepturonic AcidsThe reaction of the xylo-dialdehyde 1 with ethyl nitroacetate yields the adduct 3 which by treatment with Raney nickel in acetic anhydride leads to the chromatographically separable derivatives of 6-acetamido-6-deoxy-D-glycero-D-gluco-hepturonic acid 5 and 6-acetamido-6-deoxy-L-glycero-D-gluco-hepturonic acid 7. The configuration at C-5 of 5 and 7 was confirmed by conversion into the pyranoses 18 and 23 and analysis of their NMR spectra. The configuration at C-6 of 5 and 7 was based on the NMR data of the benzylidene derivatives 19, 20, and 24 which were accessible from 15 and 21. Stepwise deblocking reactions of compounds 5 and 7 furnish the unblocked 6-acetamido-6-deoxyheptopyranosuronic acids 27 and 30.
    Notes: Die Umsetzung des xylo-Dialdehydes 1 mit Nitroessigsäure-ethylester führt zum Addukt 3, das mit Raney-Nickel in Acetanhydrid zu den chromatographisch trennbaren Derivaten der 6-Acetamido-6-desoxy-D-glycero-D-gluco-hepturonsäure 5 und der 6-Acetamido-6-desoxy-L-glycero-D-gluco-hepturonsäure 7 führt. Die Konfigurationszuordnung an C-5 von 5 und 7 erfolgte durch Überführung in die Pyranosen 18 und 23 und Analyse ihrer NMR-Spektren. Die Zuordnung der Konfiguration an C-6 von 5 und 7 gelang durch NMR-spektroskopische Untersuchungen der über 15 und 21 darstellbaren Benzylidenverbindungen 19, 20 und 24. Durch stufenweise Entblockierung sind die freien 6-Acetamido-6-desoxyheptopyranuronsäuren 27 und 30 zugänglich.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1985 (1985), S. 1513-1536 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of Glycosides of Mono-, Sesqui-, and Diterpene AlcoholsThe β-D-glucopyranosides of the monoterpene alcohols (S)-(-)-β-citronellol (1), (S)-cis-verbenol (5), (3R)-(-)-linalool (8), dihydromyrcenol (11), terpinen-4-ol (14), of the norcarotinoides β-ionol (17), α-ionol (22), and of the sesquiterpene alcohol (+)-cedrol (27) as well as of the diterpene alcohols sclareol (33) and cis-abienol (40) have been synthesized. An α-D-glucopyranoside was obtainable from cembradiol (43). For all glycoside syntheses pyranosyl bromides have been applied as glycosyl donors. Most of the glycosylation reactions have been accomplished with silver silicate as catalyst.
    Notes: Es wurden die β-D-Glucopyranoside der Monoterpenalkohole (S)-(-)-β-Citronellol (1), (S)-cis-Verbenol (5), (3R)-(-)-Linalool (8), Dihydromyrcenol (11), Terpinen-4-ol (14), der Norcarotinoide β-Ionol (17), α-Ionol (22) und des Sesquiterpenalkohols (+)-Cedrol (27) sowie der Diterpenalkohole Sclareol (33) und cis-Abienol (40) synthetisiert. Ein α-D-Glucopyranosid war vom Cembradiol (43) erhältlich. Bei allen Glycosidsynthesen wurden Pyranosyl-bromide als Glycosyldonatoren eingesetzt. Als Katalysator wurde in der Mehrzahl der Glycosylierungsreaktionen reaktives Silbersilicat verwendet.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Conformational Analysis, XXVIII. - Conformational Analysis of Heparin-Like Di- and Trisaccharides Containing α-L-Idopyranose UnitsHighfield NMR studies and HSEA calculations were performed for the synthetic heparin-like di- and trisaccharides 1-9. Comparing the measured proton-proton coupling constants and NOE values with the calculated data lead to the conclusion, that the conformation of the idopyranose unit in the oligosaccharides is in a 1C4 ⇌ 2SO equilibrium. The state of the equilibrium strongly depends on the substitution pattern. The non-sulfated structures 1 and 3 show a high 2SO proportion at the equilibrium. By substituting a sulfate group at 2′-OH position of the idopyranose unit, this unit mainly adopts the 1C4 chair conformation, see structures 5,6 and 7. Changing an N-acetyl group for a N-sulfate group at the non-reducing glucosamine unit produces a well-balanced 1C4 ⇌ 2SO equilibrium. An NH3+ group at the same glucosamine unit fixes the idopyranose unit in a slightly deformed 1C4 conformation.
    Notes: Hochfeld-NMR-Untersuchungen und HSEA-Berechnungen werden für die synthetisierten Di- und Trisaccharide 1-9 durchgeführt, die den Sequenzen des Heparins analog sind. Die gemessenen 1H-1H-Kopplungskonstanten und NOE-Effekte führen im Vergleich mit den berechneten Daten zu dem Ergebnis, daß die Idopyranose-Einheit in den Oligosacchariden ein Konformationsgleichgewicht 1C4 ⇌ 2SO einnimmt. Die Lage des Gleichgewichtes ist in hohem Maße vom jeweiligen Substitutionsmuster abhängig. Die nichtsulfatierten Strukturen 1,3 zeigen einen hohen 2SO-Anteil am Gleichgewicht. Nach Einführung einer O-Sulfatgruppe an der 2′-OH-Gruppe der Id⊙pyranose liegt diese stark bevorzugt in der 1C4-Sesselform vor wie in 5, 6 und 7. Der Austausch einer N-Acetatgruppe an der nicht-reduzierenden Glucosamin-Einheit gegen eine N-Sulfatfunktion ergibt eine ausgewogenere Gleichgewichtseinstellung 1C4 ⇌ 2SO. Eine NH3+-Gruppe an der gleichen Glucosamin-Einheit führt zu einer leicht deformierten 1C4-Konformation an der Idopyranose-Einheit.
    Additional Material: 7 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1986 (1986), S. 814-824 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of Olivosyl-Oliosides and Spectroscopic Structure Assignment of Mithramycin1,5-Anhydro-2-deoxy-D-arabino-hex-1-entitol is transformed into the peracetylated 2,6-dideoxy-D-arabino compound 7 which by use of trimethylsilyl bromide is converted into the highly reactive glycosyl bromide 8. The glycosylation of both, the monoacetyl-2,6-dideoxy-D-lyxo derivatives 9 and 10, respectively, leads to the formation of the anomeric 1 → 3- as well as 1 → 4-linked disaccharides 11 or 13. In mithramycin decaacetate (2) all protons and carbon atoms could be assigned by the 2D-NMR technique. By comparison of the spectroscopic data of 2 and the peracetylated disaccharides 11 and 13 a β(1 → 3)-linkage in the B - A-disaccharide fragment of mithramycin is established.
    Notes: Ausgehend von 1,5-Anhydro-2-desoxy-D-arabino-hex-1-enitol wird die peracetylierte 2,6-Didesoxy-D-arabino-Verbindung 7 erhalten und mit Bromtrimethylsilan zu dem sehr reaktiven Glycosylbromid 8 umgesetzt. Glycosylierung der Monoacetyl-2,6-didesoxy-D-lyxo-Komponenten 9 oder 10 mit 8 ergibt die anomeren 1 → 4- und 1 → 3-verknüpften Disaccharide 11 und 13. Durch 2D-NMR-Messungen können alle Protonen und Kohlenstoffatome in Mithramycindecaacetat (2) zugeordnet werden. Vergleiche der spektroskopischen Daten von 2 mit denen der peracetylierten Disaccharide 11 und 13 beweisen das Vorliegen einer β(1 → 3)-Bindung im B - A-Disaccharidfragment des Mithramycins.
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  • 7
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Unusual Reaction to Glycosyl Urethanes During a Synthesis of GlycopeptidesReaction of the disaccharide halide 1 with N-(3,5-dimethoxy-α,α-dimethylbenzyloxycarbonyl)-L-serine benzyl ester (5) unexpectedly yields the glycosyl urethane 10. Glycosidation of 5 predominantly occurs at the urethane oxygen and not at the free hydroxy group of L-serine. During the formation of 10 the β-hydroxy group of serine is converted into a 3,5-dimethoxy-α,α-dimethylbenzyl ether.
    Notes: Die Umsetzung des Disaccharidhalogenids 1 mit N-(3,5-Dimethoxy-α,α-dimethylbenzyloxycarbonyl)-L- serin-benzylester (5) führt unerwartet zum Glycosylurethan 10. Im Derivat 5 wird bevorzugt der Urethansauerstoff und nicht die freie OH-Gruppe des L-Serins glycosidiert. Während der Reaktion zu 10 erfolgt Überführung der β-OH-Gruppe des Serins in einen (3,5-Dimethoxy-α,α-dimethylbenzyl)ether.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0170-2041
    Keywords: Euploea ; Danainae ; Butterflies, hairpencils ; Terpenoids ; Edulan ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Epoxytetrahydroedulan, ein neues Terpenoid aus den Haarpinseln der Schmetterlinge Euploea (Lep.: Danainae)Die Hauptkomponente der flüchtigen Inhaltsstoffe der Haarpinsel männlicher Schmetterlinge der Gattung Euploea (Danainae) wurde als 9,10-Epoxytetrahydroedulan identifiziert: 1R,2S,4S,7R,10S)-1,6,6,10-Tetramethyl-
    Notes: The main component among the volatiles from hairpencils of male danaid butterflies of the genus Euploea was found to be 9,10-epoxytetrahydroedulan: (1R,2S,4S,7R, 10S)-1,6,6,10-tetramethyl-3,11-dioxatricyclo[5.4.0.02,4]undecane (12). Identification and synthesis of the compound are described. Another edulan derivative, (1R,3S,6R)-1,3,7,7-tetramethyl-2-oxabicyclo[4.4.0]dec-9-en-8-one (13) could be identified from the hairpencils of Danaus plexippus males.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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