Angewandte Chemie International Edition in English

Cover image for Vol. 23 Issue 11

November 1984

Volume 23, Issue 11

Pages 831–918

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 11/1984)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198408311

      Thumbnail image of graphical abstract

      The cover page shows the structure of the Fe8S6Imath image ion. The eight iron atoms form an almost ideal cube; the six μ4-bonded sulfur atoms over the faces of the cube result in an almost regular dodecahedron with twelve rectangular faces. The iron atoms are coordinated in a slightly distorted tetrahedral fashion with respect to the terminal iodine atoms. The synthesis, structure, and importance of this interesting cluster ion as a model for the active center of the FeMo-protein of nitrogenase are discussed by S. Pohl and W. Saak in their communication on p. 907f.

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 11/1984)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198408312

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Cyclic Voltammetry—“Electrochemical Spectroscopy”. New Analytical Methods (25) (pages 831–847)

      Priv.-Doz. Dr. Jürgen Heinze

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198408313

      Cyclovoltammetry has become one of the most important methods in electroanalytical chemistry, largely because the technique is moderately inexpensive and evaluation of the results is relatively simple. Cyclovoltammetry not only provides information on the thermodynamics of redox processes but also on the kinetics of heterogeneous electron-transfer reactions and coupled homogeneous chemical reactions.

    2. Prostaglandin Syntheses by Three-Component Coupling. New Synthetic Methods (49) (pages 847–876)

      Prof. Dr. Ryoji Noyori and Assoc. Prof. Dr. Masaaki Suzuki

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198408471

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      Novel methods for the enantioselective reduction of prochiral carbonyl compounds, for the conjugate addition of organocopper compounds to α,β-enones, and for double vicinal CC-coupling have been developed in order to effectively realize the three-component coupling illustrated below. This strategy enables a versatile entry to natural prostaglandins and synthetic analogues.

    3. Asymmetric Diels-Alder and Ene Reactions in Organic Synthesis. New Synthetic Methods (48) (pages 876–889)

      Prof. Dr. Wolfgang Oppolzer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198408761

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      Up to four asymmetric centers with predictable relative and absolute configuration can be created in one step using the asymmetric Diels-Alder reaction. Its potential is manifested, above all, in the synthesis of natural products, e.g. (−)-β-santalene 1, a constituent of sandalwood.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Donor-Substituted Thiocarbonyl Functions as Heterodienophiles in [4+2]-Cycloadditions with Inverse Electron Demand (pages 890–891)

      Prof. Dr. Gunther Seitz, Apotheker Rolf Mohr, Dr. Wolfgang Overheu, Prof. Dr. Rudolf Allmann and Dipl.-Min. Michael Nagel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198408901

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      That Diels-Alder reactions with inverse electron demand can also be carried out with thiocarbonyl compounds has now been demonstrated for the first time using donor-substituted compounds such as 1. Their [4+2]-cycloaddition with acceptor-substituted tetrazines 2 leads via elimination of N2 to the thiadiazines 3, which, depending on the pattern of substitution, fragment more or less readily to pyrazoles and sulfur.

    2. Synthesis of a Stable Aminosilanol and a Lithium Aminosilanolate with Cubane Structure (pages 891–892)

      Onno Graalmann, Prof. Dr. Uwe Klingebiel, Dr. William Clegg, Martin Haase and Prof. George M. Sheldrick

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198408911

      Neither inter- nor intramolecular NH3- or H2O-cleavage takes place in the first stable aminosilanol 2, formed on reaction of the chlorosilanol 1 with ammonia. 2 reacts with BuLi to give 3, which is tetrameric in the gas phase and in the solid state.

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    3. Thermospray Mass Spectrometry of Diquaternary Ammonium Salts (pages 892–893)

      Günter Schmelzeisen-Redeker, Dr. Ulrich Giessmann and Prof. Dr. Franz-Wilhelm Röllgen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198408921

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      Where other new mass spectrometric methods such as SIMS, FAB, and laser desorption fail, thermospray (TSP) mass spectrometry meets with success. This gentle method for the ionization of thermally labile compounds enables the direct detection of diquaternary ammonium ions such as 1 and 2.

    4. Elementary Steps in Catalytic 1-Alkyne Coupling to Substituted Cyclooctatetraenes (pages 893–894)

      Dr. Rainer Diercks, Dipl.-Chem. Lutz Stamp, Dr. Jürgen Kopf and Prof. Dr. Heindirk tom Dieck

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198408931

      A butadienyl bridge between two nickel atoms, which, in addition, carries N ligands of the diazadiene type, is formed on reaction of mononuclear diazadienenickel complexes with disubstituted acetylenes. The pattern of substitution of the C4-bridge is the same as that of the octatetraene formed from the same educts. These findings are a further indication of binuclear catalysts in the formation of COT from alkynes.

    5. 2,7-Di-tert-butyl-1-phenyl-1H-phosphepine—The First Stable, Monocyclic Phosphepine (pages 894–895)

      Prof. Dr. Gottfried Märkl and Dipl.-Chem. Willibald Burger

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198408941

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      Reductive cyclization of the dialdehyde 1 by McMurry reaction is the key step in the synthesis of the title compound 2. According to the 1H-NMR spectrum, 2 is present in the boat conformation. The tert-butyl groups in the positions 2 and 7 hinder isomerization to the structural analogue of norcaradiene and hence also the ready thermal decomposition. R′ = Ph, R = tBu.

    6. Easy Synthesis of Phosphaalkenes by a Phosphorus-Analogous Isocyanide Reaction and an Atypical Crystal Structure of a Tetracarbonyl(phosphaalkene)iron Complex (pages 895–896)

      Prof. Dr. Rolf Appel, Carl Casser, Michael Immenkeppel and Falk Knoch

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198408951

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      Hitherto inaccessible C-halogenated phosphaalkenes 3 can now be obtained, in analogy to the long known isocyanide reaction, from the phosphane 1. Compound 3, X = Br, is the first phosphaalkene whose E- and Z-isomers have been isolated in pure form.

    7. Conformation of Glycosyl Radicals: Radical Stabilization by β-CO Bonds (pages 896–898)

      Jacques Dupuis, Prof. Dr. Bernd Giese, Daniel Rüegge, Prof. Dr. Hanns Fischer, Dr. Hans-Gert Korth and Prof. Dr. Reiner Sustmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198408961

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      A transformation from the chair- into the boat conformation takes place when glucosides such as 1 are converted into glucosyl radicals 2. This preference for the boat conformation is due to the radical-stabilizing effect of the coplanar arrangement of the β-CO bond and semi-occupied orbital. The findings are of interest regarding stereoselective radical CC-linkage in the synthesis of C-glycosides.

    8. Highly Enantioselective Homoaldol Additions with Chiral N-Allylureas—Application to the Synthesis of Optically Pure γ-Lactones (pages 898–899)

      Dipl.-Chem. Hanno Roder, Prof. Dr. Günter Helmchen, Eva-Maria Peters, Dr. Karl Peters and Prof. Dr. Hans-Georg von Schnering

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198408981

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      Numerous lactones are important pheromones, olfactories, or chiral synthetic building blocks. The enantioselective synthesis of lactones of the type 3 has now been accomplished using the readily accessible chiral allyltitanium compounds 1 and ent-1 by successive addition to aldehydes and ketones, acid hydrolysis, and oxidation.

    9. A Binuclear, Mixed-Valence MoVI/V-Complex; The Crystal Structure of [(C9H21N3)2Mo2VIO5](Br3)2 (pages 899–900)

      Prof. Dr. Karl Wieghardt, Dipl.-Chem. Gabriele Backes-Dahmann, Dipl.-Chem. Willy Herrmann and Prof. Dr. Johannes Weiss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198408991

      Chemical or electrochemical reduction of the binuclear MoVI complex ion 1 affords the mixed valence MoVI/V ion 2, which can be reduced to the MoV species 3. 2 is the first binuclear μ-oxo-bridged MoVI/V complex. Such systems are under discussion as active centers in the enzymes nitrate reductase as well as sulfite oxidase and xanthine oxidase.

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    10. [3+2]-Cycloaddition Reactions of a Stable Phosphaalkyne—Transition from Singly to Doubly Coordinated Phosphorus (pages 900–901)

      Dipl.-Chem. Wolfgang Rösch and Prof. Dr. Manfred Regitz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198409001

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      A large number of novel, five-membered phosphorus heterocycles are accessible by cycloadditions of the phosphaalkyne 1 with 1,3-dipolar compounds. Thus, reaction of 1 with diazo compounds 2 leads via intermediates 3 to formation of the novel 1H-1,2,4-diazaphospholes 4. The high reactivity of the phosphaalkyne 1 is in complete contrast to the sluggishness of nitriles.

    11. 1H-1,2,4-Diazaphospholes by [3+2]-Cycloaddition of Diazoalkanes to Phosphaalkenes (pages 901–903)

      Prof. Dr. Gottfried Märkl and Dipl.-Chem. Irene Trötsch

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198409011

      Thumbnail image of graphical abstract

      Spontaneous aromatization to the 1H-1,2,4-diazaphospholes 3 is found to occur with the primary cycloadducts 2 of the reaction of the phosphaalkene 1 with diazoalkanes. The regioselectivity of the [3+2]-cycloaddition corresponds to the polarity of the P[DOUBLE BOND]C bond. With nBuLi, the diazaphospholes 3 can be deprotonated, and the resulting anions alkylated.

    12. 1H-1,2,4-Diazaphospholes via 2-Phosphaallyl Chlorides (pages 903–904)

      Prof. Dr. Alfred Schmidpeter and Dipl.-Chem. Angela Willhalm

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198409031

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      The same P atom bonding pattern as in phosphabenzene is found in the 1H-1,2,4-diazaphospholes 1. It is therefore not surprising that 1 can be prepared in a two-step synthesis, the first step of which is reminiscent of the classical phosphabenzene synthesis.

    13. Synthesis and Structure of a (Carbene)(η2-olefin)W(CO)4 Complex (pages 904–905)

      Dipl.-Chem. Klaus Angermund, Dr. Friedrich-Wilhelm Grevels, Prof. Dr. Carl Krüger and Dipl.-Chem. Volker Skibbe

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198409041

      A strong metal-ligand π-back bonding is the reason for the trans-arrangement of carbene- and olefin-ligand in the complex 1, for which an X-ray structure analysis is available. Because of the ligand arrangement, a cyclization to the metallacyclobutane, an important intermediate in olefin metathesis, is impossible.

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    14. A Novel Entry to the Taxane Structural Unit (pages 905–906)

      Dipl.-Chem. Harribert Neh, Priv.-Doz. Dr. Siegfried Blechert, Dipl.-Chem. Wolfgang Schnick and Dipl.-Chem. Martin Jansen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198409051

      Thumbnail image of graphical abstract

      Taxanes, because of their antileukemic and antiturmoral activity, are of topical interest; they occur in plants of the Taxaceae family. The highly strained tricyclic taxane framework 1 could be constructed stereoselectively by a variant of the de Mayo reaction.

    15. Ag1.8Mn8O16: Square Planar Coordinated Ag Ions in the Channels of a Novel Hollandite Variant (pages 906–907)

      Dipl.-Chem. Fung Ming Chang and Prof. Dr. Martin Jansen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198409061

      A promising new ion-conducting material, the title compound, can be prepared from AgMnO4 and Ag2O (1:1) at 970 °C under 5 kbar O2. The Mn8O16 framework forms channel-like cavities of face-sharing cubes. The Ag ions occupy the bottle-necks of this one-dimensional diffusion channel as regular lattice sites. This constitutes the first example of square-planar coordinated Ag-ions.

    16. A Novel Iron-Sulfur Cluster with Central Fe8-Cube: Synthesis and Structure of (Et4N)3Fe8S6I8·2CH2Cl2 (pages 907–908)

      Priv.-Doz. Dr. Siegfried Pohl and Dipl.-Chem. Wolfgang Saak

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198409071

      An Fe8S6 dodecahedron with twelve rectangular faces and a central Fe8-cube is present in the novel Fe8S6Imath image ion. The synthesis of this iron-sulfur cluster ion, the structure of which is shown on the cover page, was accomplished by reaction of [Et4N][Fe6S6I6] with iron, ammonium iodide, and iodine.

    17. Structure- and Solvent-Dependence in the Complexation of Lipophilic Substrates in a Water-Soluble Azacyclophane (pages 908–910)

      Prof. Dr. Hans-Jörg Schneider, Dr. Klaus Philippi and Jürgen Pöhlmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198409081

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      After methylation to the tetraammonium salt, the azacyclophane 1 can be used as a host compound, even in neutral aqueous solutions. It has sufficient methyl groups to allow accomodation of naphthalene derivatives with continuous anti-configuration of the chain. The complexation energies can be determined by “NMR-shift titration”. X=NMe2Cl.

    18. Thin Layer Chromatography with an Immobilized Azacyclophane Derivative as Analytical Agent and Probe for Host-Guest Interactions (pages 910–911)

      Prof. Dr. Hans-Jörg Schneider, Dr. Walter Müller and Detlev Güttes

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198409101

      The macrocycle 1 immobilized on silica gel layers (see previous communication) provides new insights into host-guest interactions. The selective inclusion of an organic neutral molecule in the cavity of the macrocycle rests, on the one hand, on the interaction between lipophilic moieties of host- and guest-molecule and, on the other, on the electrostatic attraction between polar substituents in the substrate and the positive charges in the host.

    19. An Azacyclophane Derivative as Catalyst of Substrate- and Product-Selective Reactions with Ambident Anions (pages 911–912)

      Prof. Dr. Hans-Jörg Schneider and Dipl.-Chem. Rainer Busch

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198409111

      An increase in reaction rate and alteration of the product ratio in nucleophilic exchange reactions is achieved when the azacyclophane 1 described in the two previous communications is added to the reaction of ambident nucleophiles with 2-bromomethylnaphthalene. Similarly as in the case of enzymes, saturation kinetics and competitive inhibition are observed as well as substrate and product selectivity.

    20. Isocyanide Insertion into a Uranium-Carbon Double Bond (pages 912–913)

      Prof. Dr. Roger E. Cramer, Dr. K. Panchanatheswaran and Prof. Dr. John W. Gilje

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198409121

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      The red crystalline azauranacyclopropene 3—stable for months under an inert gas or in vacuo—is formed in 53% yield on reaction of the carbeneuranium complex 1 with cyclohexyl isocyanide 2. Compound 3 is the first completely characterized product of insertion of an isocyanide into a metal-carbon double bond.

    21. Di-(μ-amido)dirhodium Complexes: Structure of [Rh2(μ-(NH)2naphth)I2(CO)2(PPh3)2] (pages 913–914)

      Prof. Dr. Luis A. Oro, Dr. Maria J. Fernández, Dipl.-Chem. Javier Modrego, Dr. Concha Foces-Foces and Dr. Felix H. Cano

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198409131

      A Novel class of binuclear amido complexes containing doubly deprotonated 1,8-diaminonaphthalene as a bridging bisdihapto ligand has now been synthesized. The title compound is formed by successive reaction of [Rh(acac)(CO)2] with 1,8-C10H6(NH2)2, PPh3 and I2, whereby all intermediates have been isolated.

    22. Oligocyclic Hetarenes with Quinonoid Structure; Synthesis by Sequential Cyclizing Condensation (pages 914–915)

      Prof. Dr. Richard P. Kreher and Dipl.-Ing. Jürgen Pfister

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198409141

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      The cyclizing condensation of hetero- and carbocyclic 1,2-dicarbaldehydes such as 1 with 1,2-difunctional CH-acidic compounds can be used on the “building-block principle” for the synthesis of oligocyclic hetarenes, e.g. 2 and 3. In contrast to the parent compound 2H-isoindole, such annelated systems are thermally remarkably stable but in principle react the same way, e.g. in cycloadditions.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Book Review: Carbanion Chemistry. By R. B. Bates and C. A. Ogle (page 916)

      Dieter Hoppe

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198409161

    2. Book Review: Dynamic NMR Spectroscopy. By J. Sandström (pages 916–917)

      Martin Feigel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198409162

    3. Book Review: Membranbiochemie. By H. Sandermann (page 917)

      H.-J. Galla

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198409171

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