Angewandte Chemie International Edition in English

Cover image for Vol. 24 Issue 1

January 1985

Volume 24, Issue 1

Pages 1–76

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 1/1985)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500011

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      The cover page shows the highly symmetrical cluster [[C5Me5]3Re3O6]2⊕, which forms surprisingly readily from the trioxo half-sandwich complex [[C5Me5]Re3O3] and PPh3 in aerated tetrahydrofuran. M3O6 structural groups of this kind were hitherto unknown. ReOmath image is formed as the counterion. The salt—blue-green crystals—is stable towards oxygen. Further details are reported by W. A. Hermann et al. on p. 50.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    1. Double Asymmetric Synthesis and a New Strategy for Stereochemical Control in Organic Synthesis (pages 1–30)

      Prof. Dr. Satoru Masamune, Dr. William Choy, Dr. John S. Petersen and Lawrence R. Sita

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500013

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      In the reaction of an enantiomerically pure substrate with an enantiomerically pure reagent, two cases can be distinguished. For example, the formation of the diastereomer 3 from the substrate S-1 and the reagent S-2 (“matched pair”) is highly preferred; the reaction of S-1 with R-2 (“unmatched pair”), on the other hand, leads to a product ratio of only 1 : 1.5. This phenomenon can be analyzed as a function of the simple asymmetric reactions of S-1 and S-2 with achiral partners. A rule that qualitatively relates all of these results is the basis of a new, reagent-controlled strategy for the directed synthesis of compounds with many chiral centers. This strategy has great advantages over the classical, substrate-controlled approaches and has already proved useful in the synthesis of complex natural products.

    2. Chemical Basis of the Action of Glyoxalase I, an Anticancer Target Enzyme (pages 31–44)

      Dr. Kenneth T. Douglas and Seiji Shinkai

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500311

      A proton transfer, and not a hydride transfer, is the key step in the reaction catalyzed by glyoxalase I. This enzyme converts the adduct obtained from methylglyoxal and glutathione (GSH) into S-D-lactoylglutathione. Knowledge of its mechanism should make possible the synthesis of tailor-made inhibitors; the inhibition of glyoxalase I in cell cultures can be useful, at least in the screening of anticancer agents.—S-D-lactoylglutathione is eventually cleaved by glyoxalase II into GSH and D-lactic acid.

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  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    1. A Simple Notation System for Transition-Metal Clusters (pages 45–46)

      Dr. Tien-Yau Luh, Dr. Henry N. C. Wong and Dr. Brian F. G. Johnson

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500451

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      The description of the spatial arrangement of metal atoms and ligands in metal clusters is possible by a notation system based on the Föppl notation. Thus, for example, the structure of Co4(CO)121 is described by [1:3]-[(3):6′:3].

    2. Hydrogenobyrinic Acid and Vitamin B12 (pages 46–47)

      Dr. Trutz E. Podschun and Dr. Gerhard Müller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500461

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      Does hydrogenobyrinic acid 1 play a significant role in the biosynthesis of vitamin B12? The cobalt-free analogue 1 of the vitamin-B12 precursor cobyrinic acid cannot be converted into cobyrinic acid with enzyme preparations which catalyze the incorporation of cobalt. Hence, the answer to the above question is no, and the problem of when the cobalt ion becomes incorporated in the formation of vitamin B12 remains unsolved (R [DOUBLE BOND] H).

    3. Direct Enantiomer Resolution of Hydroxy and Carbonyl Compounds by Gas Chromatography on Chirasil-Val (pages 48–49)

      Dr. Bernhard Koppenhoefer, Dipl.-Chem. Hans Allmendinger and Graeme Nicholson

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500481

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      Enantiomers with free hydroxy groups are easily separated on peptide phases such as Chirasil-Val using well-deactivated glass capillaries. Even one hydrogen bond with the stationary phase can lead to satisfactory discrimination of the enantiomers. This technique can be applied to chiral active substances such as 1, which is used as a suicide substrate for the inhibition of hormone production in parasites (R [DOUBLE BOND] CH2F).

    4. Photooxidation of Chloroform: Isolation and Characterization of Trichloromethyl Hydroperoxide (page 50)

      Dr. Siegmar Gäb and Dr. Walter V. Turner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500501

      Trichloromethyl hydroperoxide 1 is unexpectedly stable; this discovery is of importance for the photooxidative degradation of organochlorine compounds in the atmosphere. 1 is formed upon irradiation of O2-saturated chloroform with sunlight; it reacts with N2O5 to give 2 and with acetyl chloride to give the perester 3.

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    5. Reductive Trimerization of the Trioxo Half-Sandwich Complex [(η5-C5Me5)ReO3] with Deoxygenation: The Electron-Deficient Cluster Ion [(η5-C5Me5)3Re3(μ-O)6]2+ (pages 50–52)

      Prof. Dr. Wolfgang A. Herrmann, Dr. Ricardo Serrano, Prof. Dr. Manfred L. Ziegler, Dr. Heike Pfisterer and Dr. Bernd Nuber

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500502

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      A novel M3O6 skeletal geometry is shown by the cluster cation of the perrhenate 1. The six oxygen atoms form a trigonal prism whose three rectangular faces are each symmetrically bridged by a rhenium atom. The cluster cation is, with only 46 valence electrons, an electron-deficient species.

    6. Synthesis of 3′-C-Methyl-2′-deoxyribonucleoside with Methylmagnesium Iodide (pages 52–53)

      A. Grouiller, H. Essadiq, H. Pacheco, S. Juntunen and J. Chattopadhyaya

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500521

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      The synthesis of the nucleoside 1, which contains a branched sugar, is of interest in view of the biological activities of the corresponding ribofuranosyl derivatives. The precursor, which was converted into 1 by detritylation, was formed stereoselectively as the erythro isomer on addition of methylmagnesium iodide to 2′-O-tosyl-5′-O-trityluridine.

    7. Phosphaalkenylrhenium Complexes—a Novel Class of Substances with P[DOUBLE BOND]C Bonding (pages 53–54)

      Priv.-Doz. Dr. Lothar Weber and Dipl.-Chem. Klaus Reizig

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500531

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      A simple entry to η1-bonded phosphaalkenly complexes 3 is provided by the reaction of 1 with LiPR(SiMe3). The intermediates 2 can be detected spectroscopically. 3, R [DOUBLE BOND] SiMe3 or Ph, is assingned the E-configuration (see formula) based on the 13C-NMR data; 3, R [DOUBLE BOND] tBu, on the other hand, has, according to the X-ray structure analysis, the Z-configuration.

    8. Crystal Structures of Potassium Ozonide and Rubidium Ozonide (pages 54–55)

      Dipl.-Chem. Wolfgang Schnick and Prof. Dr. Martin Jansen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500541

      Bond systems with uneven numbers of electrons—such as the ozonide ion—are an exception to the rule for main group elements and have time and again attracted the attention of experimental and theoretical chemists. Nonetheless, the exact structural data for Omath image in KO3 and RbO3 have only now been determined. The averaged bond lengths (135.7(5) and 134.1(15) pm, respectively) and bond angles (113.4(8) and 114.6(13)°, respectively) of the two ozonides agree within the standard deviations.

    9. Destabilized 2-Norbornyl Cations (pages 55–56)

      Prof. Dr. Wolfgang Kirmse, Dipl.-Chem. Uwe Mrotzeck and Dr. Rainer Siegfried

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500551

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      Four acceptor substituents at C-5 and C-6 destabilize the non-classical structure of the 2-norbornyl cation. The Wagner-Meerwein rearrangement of 1 to 2 is completely forestalled by such a substitution pattern; however, 1 undergoes an exo, exo-3,2-H shift to give 3.

    10. Nitrile Imines: Thermal Generation, Direct Observation, and Subsequent Trapping (pages 56–57)

      Prof. Dr. Curt Wentrup, Dipl.-Chem. Stephan Fischer, Prof. Dr. André Maquestiau and Dr. Robert Flammang

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500561

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      The first thermally generated nitrile imine, the species 2 (g) with non-isomerizing N-substituents, was generated from the tetrazole 1 by vacuum flash pyrolysis and characterized by mass spectrometry and IR spectroscopy. Both gaseous 2 (g) and 2 (s) isolated in a matrix can be trapped by cycloadditions.

    11. Preparation, Magnetism, and Crystal Structures of the Tautomers [LCu(μ2-OH)2CuL](ClO4)2 (Blue) and [LCu(μ2-OH2)(μ2-O)CuL](ClOμ42 (Green): μ-Aqua-μ-oxo vs. Di-μ-hydroxo Linkage (pages 57–59)

      Dr. Phalguni Chaudhuri, Dipl.-Chem. Dirk Ventur, Prof. Dr. Karl Wieghardt, Eva-M. Peters, Dr. Karl Peters and Prof. Dr. Arndt Simon

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500571

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      The first example for μ-aqua-μ-oxo bridging of two transition-metal centers is the cation of 2. This compound is formed as green crystals from CuCl2·2H2O and L in methanol after addition of aqueous NaClO4 solution. 2 is ferromagnetic. 1, the cation of which belongs to a frequently encountered type, is formed as blue crystals from Cu(ClO4)2·6H2O and L in water. 1 is antiferromagnetic. Surprisingly, in the crystal the two tautomers have the same space group and very similar structures.

    12. Quantitative HPLC Analysis and Thermodynamics of Sulfur Melts (pages 59–60)

      Prof. Dr. Ralf Steudel, Dipl.-Chem. Reinhard Strauss and Lothar Koch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500591

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      The quantitative composition of quenched sulfur melts, which had been equilibrated at 116–387°C, was determined by HPLC analysis. The melts contain ring molecules from S6 to S23. From the temperature dependence of the equilibrium constants Kc=[Sn]/[S8]n/8, the enthalpies ΔH of the 18 equilibrium reactions (1) were calculated. These are the first thermodynamic data for sulfur molecules containing more than ten atoms.

    13. A Novel Transformation of a Calicene to an Azulenofulvene (pages 60–61)

      Prof. Dr. Zen-ichi Yoshida, Mitsuhiro Shibata, Eiji Ogino and Dr. Toyonari Sugimoto

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500601

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      A novel skeletal rearrangement is involved in the formation of the azulene derivative 3, which is formed along with 4 on reaction of the calicene 1 with the fulvene 2. 3 contains a previously unknown π-electron structure.

    14. Probing the Structure and Crystallinity of a Lithium Silicate Glass by 29Si Magic-Angle-Spinning NMR Spectroscopy (pages 61–62)

      Prof. Dr. C. N. R. Rao, Prof. Dr. John M. Thomas, Dr. Jacek Klinowski, U. Selvaraj, Dr. K. J. Rao, Dr. G. Robert Millward and Dr. Subramaniam Ramdas

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500611

      The short-range order in noncrystalline and crystalline silicates can be investigated with 29Si magic-angle-spinning (MAS) NMR spectroscopy. Different 29Si chemical shifts are observed depending on the degree of cross-linkage of the silicate, the Si[BOND]O[BOND]Si bond angles, and the interatomic distances. In this way, the distribution of Si[BOND]O[BOND]Si angles in glasses, the crystallinity of which lies between 0 and 100%, can be obtained.

    15. Photooxygenolysis of Vitamin B12 (pages 62–64)

      Dr. Bernhard Kräutler and René Stepánek

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500621

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      Vitamin B12 is degraded by singlet oxygen (1O2) to the secocobamide 1. This reaction is of interest because of the medicinal and biological role played by 1O2 and provides a simple entry to secocorrinoid cleavage products of vitamin B12.

    16. Axial Chirality can lead to Chiral Smectic and Cholesteric Liquid Crystals (pages 64–65)

      Prof. Dr. Guy Solladié and Richard G. Zimmermann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500641

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      Optically active liquid crystalline compounds, whose chirality is due to molecular asymmetry—a dihedral angle of 90° between the two parts of the molecule—are existent in the cyclohexylidene ethanones 1. Such compounds could, e.g., find application as additives to nematic liquid crystals for display devices.

    17. Short Synthesis of Cerebrosides (pages 65–66)

      Prof. Dr. Richard R. Schmidt and Rudolf Kläger

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500651

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      Use of the trichloroacetimidate method for the synthesis of cerebroside has reduced the number of reaction steps and increased the yields. The key step is the reaction of the 1-O-unprotected D,L-ceramides with a trichloroacetimidate to give the D-glucocerebrosides DL-1 and DD-1, which can be quantitatively deblocked to produce DL-2 and DD-2 (natural product).

    18. Synthesis and Structure of [(C5H5)3M3(CO)63-As)] (M [DOUBLE BOND] Mo, W), Transition-Metal-Stabilized Arsanetriyl Compounds (pages 66–67)

      Klaus Blechschmitt, Dr. Heike Pfisterer, Thomas Zahn and Prof. Dr. Manfred L. Ziegler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500661

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      The missing member of the series AsnMo4–n (n = 0–4), the cluster AsMo3, is contained in compound 1. It is prepared by reaction of [(C5H5)(CO)3Mo]2 with metallic arsenic. The reaction also succeeds with the analogous tungsten compound.

    19. c-TiS2, a New Modification of Titanium Disulfide with Cubic Structure (pages 67–68)

      Prof. Dr. Robert Schöllhorn and Dipl.-Chem. Andreas Payer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500671

      A metastable modification of TiS2 has been prepared by a topotactic solid-state reaction at room temperature in which CuTi2S4 working electrodes were anodically oxidized in aprotic copper(I) electrolytes. On the basis of X-ray powder data, it can be determined that the new phase belongs to a very seldom AB2 structural type. This cubic TiS2 is of interest, inter alia, as a material for reversible electrodes in secondary batteries. It has advantages over hexagonal TiS2 (layer lattice).

    20. Novel Aspects of the Coordination Chemistry of Phosphane (pages 68–70)

      Prof. E. A. V. Ebsworth and R. Mayo

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500681

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      The complex cation 1 containing the ligands PH2 and PH3 is formed above 230 K from the precursor [Ir(CO)(PEt3)2(P′H3)2]⊕ by internal oxidative addition. Protonation and deprotonation reactions show that the basicity of the PH2 group depends on the nature of the trans-ligand.

    21. [CuCo(CO)4]n—Crystal Structure of a Polymer with a One-Dimensional, Infinite Copper-Cobalt Bonding System (pages 70–71)

      Dr. Peter Klüfers

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500701

      CuCo(CO)4 crystallizes dimorphically. The tetramer with a Cu4Co4 eight-membered ring (orange-red crystals) is known: new is the polymer with Cu[BOND]Co zig-zag chains (strongly distorted yellow platelets or needles that separate into fibers). Interatomic distances and bond angles in the building blocks of the chains are almost the same as in the tetrameric modification.

    22. Synthesis and Structure of a Thallium Complex with an Anionic Sandwich Complex Ligand (pages 71–72)

      Klaus Stumpf, Dr. Hans Pritzkow and Prof. Dr. Walter Siebert

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500711

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      The first sandwich complex with an apical thallium atom, 1, is made up of the layers C5H5/Co/Me4(B2C3)H2/Tl. In contrast to polymeric Tl(C5H5), 1 is a discrete molecule described as a closo-cluster.

    23. (C6H5Sb)6·(1,4-dioxane), the First Cyclohexastibane (pages 72–73)

      Priv.-Doz. Dr. Hans Joachim Breunig, Dipl.-Chem. Karl Häberle, Prof. Dr. Martin Dräger and Dipl.-Chem. Tevfik Severengiz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500721

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      A ring of six antimony atoms is contained in the title compound; it is the first of its type. Earlier attempts to synthesize it usually led to formation of solid polymers. 1 is formed when PhSb(SiMe3)2 in 1,4-dioxane is oxidized by air. According to the X-ray structure analysis no specific interactions occur between dioxane and Sb.

    24. A Novel Rearrangement in (R2S∴SR2)-Radical Cations with a 3e-Bond (pages 73–74)

      Dipl.-Chem. Roland Goslich, Dr. Joachim Weiss, Dr. Hermann J. Möckel, Dr. Jörg Mönig and Prof. Dr. Klaus-Dieter Asmus

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500731

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      The stabilization of the radical cation 1, with a three-electron bond, is reminescent of the Wittig and Stevens rearrangements. In the rearrangement of 1 to Et[BOND]S[BOND]S[BOND]Et, H⊕ and H are formally split off. This reaction takes place only for high concentrations of 1; it is noteworthy that oxygen doesn't affect the yield.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
  4. Corrigenda

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    1. You have free access to this content
      Corrigendum (page 76)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198500761