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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 337 (1995), S. 113-124 
    ISSN: 0941-1216
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydrogen abstraction of radical intermediates yielded by radical addition to the methylene compound 6, shows excellent facial selectivity. Conformational analyses of the radical intermediates were carried out by quantum chemical calculations and explain these results. The chiral radicals 7 and 8, yielded from the chiral bromides 3 and 4, lead with ethyl acrylate to the adducts 28 and 29 with more 96% de. The adduct 28 was converted to the optically active γ-valerolactone 30. The structures of the bromides 3, 4 and 31 as well as the radical adducts 19a, 24 and 25 have been verified by X-ray diffraction analysis.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1183-1195 
    ISSN: 0044-2313
    Keywords: Zinc complexes ; imidazole ; imidazoline ; bisimidazoline complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zinc Coordination Compounds with Imidazoline and Imidazole Donor Ligands.By reaction of the two bidentate bisimidazoline ligands 1,2-bis(2-imidazoline-2-yl)ethan (BIE) and 1,2-bis(2-imidazoline-2-yl)benzene (BIB) with zinc bromide under various reaction conditions the complexes [ZnBr2(BIE)] (1), [ZnBr2(BIB)] (2), [Zn(BIE)2]Br2 (3) and [Zn(BIB)2](BPh4)2 (4) were synthesized and characterized. In all compounds the zinc atom is tetrahedrally coordinated, either by a bidentate ligand and two bromine ligands, or by two of the chelate ligands. Zn—N—bond distances for 1-4 range from 1.966(2) to 2.013(3) Å, and the Zn—Br distances from 2.372(1) to 2.403(1) Å. [3-(imidazole-1-yl)-1-oxopropyl]benzene (IOB) was prepared as a novel imidazole ligand which carries a keto-O atom in 1,5-position to the pyridine-N atom. The zinc in [ZnCl2(IOB)2] (5) is coordinated by two ligands and two Cl atoms forming a distorted tetrahedral ZnN2Cl2 unit (Zn—N: 2.013(3) and 2.029(2) Å; Zn—Cl: 2.226(1) and 2.242(1) Å).The colourless compounds 1-5 were characterized by IR, 1H-NMR, X-ray absorption spectra and single-crystal X-ray structure analysis. Space groups and structural data: 1: P21/c, a = 7.717(2), b = 22.814(5), c = 8.026(2) Å, β = 117.58(2)° (140 K), R = 0.0283; 2: Cc, a = 11.831(3), b = 11.677(1), c = 11.846(1) Å, β = 114.55(2)°, R = 0.0237; 3: P42/n, a = 7.931(1), c = 16.945(1) Å, R = 0.0312; 4: P21/c, a = 18.666(2), b = 16.615(2), c = 19.786(2) Å, β = 99.17(1)°, R = 0.0472; 5: P21/c, a = 9.173(2), b = 9.230(1), c = 28.357(3) Å, β = 96.63(1)°, R = 0.0317.
    Notes: Durch Umsetzungen der zweizähnigen Bisimidazolin-Liganden 1,2-Bis(2-imidazolin-2-yl)ethan (BIE) und 1,2-Bis(2-imidazolin-2-yl)benzol (BIB) mit Zinkbromid unter verschiedenen Reaktionsbedingungen konnten die Komplexverbindungen [ZnBr2(BIE)] (1), [ZnBr2(BIB)] (2), [Zn(BIE)2]Br2 (3) und [Zn(BIB)2](BPh4)2 (4) synthetisiert und charakterisiert werden. Das Zinkatom ist jeweils tetraedrisch von einem zweizähnigen Chelatliganden und zwei Bromatomen oder von zwei dieser Liganden koordiniert. Die Zn—N-Bindungslängen in 1-4 variieren zwischen 1,966(2) und 2,013(3) Å, für die Zn—Br-Abstände wurden Werte zwischen 2,372(1) und 2,403(1) Å beobachtet. Mit dem neuen Liganden [3-(Imidazol-1-yl)-1-oxopropyl]benzol (IOB) gelang die Synthese des Komplexes [ZnCl2(IOB)2] (5), in dem eine tetraedrische ZnN2Cl2-Koordinationseinheit vorliegt (Zn—N: 2,013(3) und 2,029(2) Å; Zn—Cl: 2,226(1) und 2,242(1) Å).Die farblosen Verbindungen 1-5 wurden durch IR-, 1H-NMR- und Röntgenabsorptionsspektren sowie durch vollständige Röntgenstrukturanalysen charakterisiert. Raumgruppen und Gitterkonstanten: 1: P21/c, a = 7,717(2), b = 22,814(5), c = 8,026(2) Å, β = 117,58(2)° (140 K), R = 0,0283; 2: Cc, a = 11,831(3), b = 11,677(1), c = 11,846(1) Å, β = 114,55(2)°, R = 0,0237; 3: P42/n, a = 7,931(1), c = 16,945(1) Å, R = 0,0312; 4: P21/c, a = 18,666(2), b = 16,615(2), c = 19,786(2) Å, β = 99,17(1)°, R = 0,0472; 5: P21/c, a = 9,173(2), b = 9,230(1), c = 28,357(3) Å, β = 96,63(1)°, R = 0,0317.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0044-2313
    Keywords: Zinc complex ; iron complex ; tripodal ligand ; benzimidazole ; imidazole ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Tripodliganden: Darstellung verzerrter Koordinationspolyeder in biomimetischen Metallkomplexen. Kristallstrukturen von [Zn(SCN)(ntb)](SCN) · iPrpOH und [Fe(acac)(ntb)](ClO4)2 · 2 CH2Cl2 · iPrpOH, ntb = N-Tris(2-benzimidazolylmethyl)aminDer Tripodligand N-Tris(2-benzimidazolylmethyl)amin (ntb) wurde zur Synthese eines Zink(II)- und eines Eisen(III)-Komplexes, [Zn(SCN)(ntb)](SCN) · iPrpOH (1) und [Fe(acac)(ntb)](ClO4)2 · 2 CH2Cl2 · iPrpOH (2), eingesetzt. Der Zinkkomplex hat eine stark verzerrte trigonal-bipyramidale Koordinationssphäre. Die koordinierenden Atome sind ein Amin-N, drei Benzimidazol-N und ein SCN--N-Atom. Auffällig hier ist der 2.539(6)Å große Zn—Namin-Bindungsabstand. Das Koordinationspolyeder des Eisenkomplexes ist weniger stark verzerrt als das in 1 und wird von einem Amin- und drei Benzimidazol-Stickstoffatomen des Liganden sowie zwei Sauerstoffatomen des Acetylacetonats gebildet. Die Fe—O-Bindungslängen zeigen eine Differenz von ca. 0.1 Å, die wie die ungewöhnlich lange Zn—N-Bindung durch einen Trans-Effekt verursacht wird. 1 kristallisiert triklin in der Raumgruppe P1 mit: a = 9.530(1), b = 13.402(1), c = 13.578(2)Å, α = 98.83(1), β = 95.19(1), γ = 101.21(1)°, Z = 2; 2 ist ebenfalls triklin, P1, mit: a = 9.875(6), b = 12.929(10), c = 18.635(15)Å, α = 94.95(8), β = 101.01(6), γ = 111.09(4)°, Z = 2.
    Notes: The tripodal ligand N-tris(2-benzimidazolylmethyl)-amine (ntb) was used for the preparation of zinc(II) and iron(III) complexes, [Zn(SCN)(ntb)](SCN) · iPrpOH (1) and [Fe(acac)(ntb)](ClO4)2 · 2CH2Cl2 · iPrpOH (2). 1 has a highly distorted trigonal-bipyramidal ZnN5 coordination geometry. The donor atoms are nitrogens of one amine, three benzimidazoles and one SCN-. A striking feature of the complex is the length of the Zn—Namine bond of 2.539(6)Å. The octahedral N4O2 coordination sphere of the iron in 2 is less distorted than that of the zinc in 1. The metal is surrounded by an amine and three benzimidazole nitrogens of the ligand and two oxygens of the bidentate acetylacetonate co-ligand. The Fe—O bond lengths differ by about 0.1 Å. As for the unusual long Zn—N bond in 1 this is a result of a trans effect. 1 crystallizes in the space group P1 with: a = 9.530(1)Å, b = 13.402(1)Å, c = 13.578(2)Å, α = 98.83(1), β = 95.19(1), γ = 101.21(1)°, Z = 2; 2 is also triclinic, space group P1, with: a = 9.875(6)Å, b = 12.929(10)Å, c = 18.635(15)Å, α = 94.95(8)°, β = 101.01(6)°, γ = 111.09(4)°, Z = 2.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1985 (1985), S. 1437-1447 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Studies on the Synthesis of Mitomycins, 4.- Elucidation of the Configuration of Mitosane DerivativesThe configurations of the mitosane derivatives described in the previous communications1) were established by spectroscopic investigations and X-ray analysis of rac-1e.
    Notes: Die Konfigurationen der in den vorstehenden Arbeiten beschriebenen Mitosan-Derivate wurden durch spektroskopische Untersuchungen und eine Röntgenstrukturanalyse der Verbindung rac-1e bewiesen.
    Additional Material: 2 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1988 (1988), S. 695-704 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Diastereoselective Syntheses of rac-Slaframine and rac-6-epi-SlaframineIndolizidinones 8 have been obtained from thalidomide (5) and cyclopropylphosphonium salts 6 in good yields. Acid-catalyzed rearrangement of 8a gave the isomer 11. A regio- and stereoselective acetoxylation of 8a and 11 was achieved with lead tetraacetate: using standard conditions, acetates 15 and 16 were obtained; in the presence of triethylamine, however, 8a has been transformed into the acetoxy derivative 17. rac-6-epi-Slaframine (4) and rac-slaframine (1) were obtained from acetates 16 and 17 on conventional routes.
    Notes: Indolizidinone 8 wurden aus Thalidomid (5) und Cyclopropylphosphoniumsalzen 6 in guten Ausbeuten erhalten. 8a ließ sich mit Säuren zu 11 isomerisieren. Eine regio- und stereoselektive Acetoxylierung von 8a und 11 gelang mit Blei(IV)-acetat: unter den üblichen Bedingungen entstanden die Acetate 15 und 16; in Gegenwart von Triethylamin reagierte 8a jedoch zum Acetoxyderivat 17. rac-6-epi-Slaframin (4) und rac-Slaframin (1) wurden aus 16 und 17 auf konventionellen Wegen erhalten.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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