Angewandte Chemie International Edition in English

Cover image for Vol. 20 Issue 8

August 1981

Volume 20, Issue 8

Pages 617–702

Currently known as: Angewandte Chemie International Edition

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    1. The Philosophy of Science: Its Possibilities and Limits (pages 617–623)

      Prof. Dr. Wolfgang Wieland

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106173

      The main stages in development of the modern philosophy of science can be portrayed as a trilogy and satyrical play; these stages can be marked by the “Vienna Circle” and the names Karl R. Popper, Thomas B. Kuhn, Paul K. Feyerabend.

    2. Mass Spectrometry of Negative Ions (pages 624–637)

      Prof. Dr. Herbert Budzikiewicz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106241

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      What information can be gained by the mass spectrometry of negative ions? Has it importance in structure elucidation and the analysis of mixtures of organic compounds? Are there any general rules? The paper gives answers to these and many other questions (right: NI spectrum of anisole).

    3. Structure and Decay of Gaseous Organic Radical Cations Studied by Their Radiative Decay, Exemplified by the 1,3-Pentadiyne Cation (pages 638–646)

      Dr. John P. Maier

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106381

      Electronically excited organic radical cations of several types decay radiatively. Their structure and relaxation can be probed in detail using emission, laser induced fluorescence and photoelectron-photon coincidence techniques. An illustrative example is pro-pided by the 1,3-pentadiyne cation.

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    4. Methods of Fluorination in Organic Chemistry (pages 647–667)

      Michael R. C. Gerstenberger and Prof. Dr. Alois Haas

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106471

      The spectrum of changes the fluorine substituents can bring about in organic molecules extends from extreme stabilization (e. g. in polymers and blood-substitutes) to drastic increases in reactivity (e. g. in Pharmaceuticals).—A selection of fluorinating agents is given below.

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  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    1. Facile Synthesis of Racemic Cysteine (page 668)

      Dr. Jürgen Martens, Dr. Heribert Offermanns and Dr. Paul Scherberich

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106681

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      Economical raw materials such as ammonia and acetone are the educts of a new total synthesis of racemic cysteine (2), which is obtained in good yields in a few steps via (1) and its HCN adduce.

    2. New Tungsten-Iridium Dinuclear Complexes Containing Cyclopentadienyl and Hydrido Bridges (pages 668–669)

      Dr. Paul S. Pregosin, (Ciba-Geigy-Fellow) Antonio Togni and Prof. Dr. Luigi M. Venanzi

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106682

      Thumbnail image of graphical abstract

      The green, air-stable tungsten-iridium dinu-clear complex (1), L = PEt3, is the first species known to contain C5Hmath image and H together as bridging ligands. Its structure is secured by NMR data.

    3. Double Ring-Opening of Bicyclic Oxaziridines to N-(3-Oxopropyl)amides by Iron(II) Sulfate (pages 669–670)

      Dr. David St. C. Black and Lynn M. Johnstone

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106691

      Thumbnail image of graphical abstract

      A favorable method for the synthesis of the oxoamides (2), X = H2 or O, is the opening of the bicyclic oxaziridines (1) with FeSO4. Some observations support the assumption that the reaction proceeds via radicals.

    4. Three-Atom Ring Expansion of Cyclic Ketones via Nitrones and Oxaziridines (pages 670–671)

      Dr. David St. C. Black and Lynn M. Johnstone

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106701

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      Eight- and nine-membered ring oxolactams (2) can be prepared by FeSO4-induced ring-opening of tricyclic oxaziridines. The intermediate is accessible in two ways from cyclic ketones (1).

    5. Formation of Oxiranes from Methyl(phenyl)selenoniomethanide and Aldehydes or Ketones (pages 671–672)

      Dr. Ken Takaki, Dipl.-Chem. Masateru Yasumura and Prof. Dr. Kenji Negoro

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106711

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      The synthesis of oxiranes (2) from the non-stabilized selenium ylide (1) and ketones or aromatic aldehydes has been accomplished in 80–90% yields under mild conditions. In contrast heptanal does not react with (1).

    6. Experimental Evidence for the [H2SSH2] Radical Cation in Solution (pages 672–673)

      Dr. Shamim A. Chaudhri and Prof. Dr. Klaus-Dieter Asmus

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106721

      Pulse radiolysis of an aqueous H2S-solution leads to formation of the radical cation [H2SSH2] This species, which absorbs at 370 nm, has a three-electron S[BOND]S bond in which two electrons form a σ-bond; the third electron resides in an antibonding σast;-orbital.

    7. An ab initio Investigation of the Mechanism of Ester Reduction (pages 673–674)

      Pietro Cremaschi, Gabriele Morosi and Prof. Dr. Massimo Simonetta

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106731

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      The radical anion of methyl formate dissociates with cleavage of the Calkyl[BOND]O bond (a) According to ab-initio calculations a system about 40 kcal/mol more stable than in the rupture of the Ccarbonyl[BOND]O bond (b) is formed.

    8. Addition of Olefins to 2,5-Diphenyl-1,3,4-oxadiazin-6-one (pages 674–675)

      Prof. Dr. Manfred Christl, Dipl.-Chem. Ulrike Lanzendörfer and Dipl.-Chem. Silke Freund

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106741

      Thumbnail image of graphical abstract

      Cycloadditions of the oxadiazinones (1) with benzvalene, norbornene, norbor-nadiene, cyclopentene, and styrene yield primary products of the formal addition of benzoyl- and a phenylketenyl-group to the double bond, which then react further–in the case of benzvalene to the tetracycle (2).

    9. Valence Isomerization of an Imino(methylene)phosphorane to a 1,2λ3-Azaphosphiridine: A Novel Rearrangement in the Phosphorus System (pages 675–677)

      Prof. Dr. Edgar Niecke, Dipl.-Chem. Anette Seyer and Dirk-Andreas Wildbredt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106751

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      The thermal rearrangement of the N-alkyl-ated amino(imino)phosphorane (1) into the three-membered ring (2) is a surprising reaction, for N-silylated analogues of (1) form diiminophosphoranes by 1,3-shift of a silyl group. (R = iPr, R′ = tBu)

    10. Pterodactyladiene (Tetracyclo[4.4.0.02,5.07.10]deca-3,8-diene) (pages 677–678)

      Prof. Dr. Hans-Dieter Martin, Dipl.-Chem. Bernhard Mayer, Marianne Pütter and Dipl.-Chem. Hans Höchstetter

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106771

      Thumbnail image of graphical abstract

      A new (CH)10-hydrocarbon, the title compound (1), was obtained from acetylene and maleic anhydride in a multistep reaction. For derivatives there were already other synthetic methods, but they could not be applied to the parent compound.

    11. Periodated Cyclosilanes (page 678)

      Prof. Dr. Edwin Hengge and Dr. Dieter Kovar

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106781

      The first cyclic silicon-iodine compounds (SiI2)n, n = 4, 5, 6, are accessible from the corresponding phenyl derivatives by reaction with HI in the presence of A1I3 catalyst. The catalyst must be free of water and iodine. The products are yellow and extremely sensitive to moisture.

    12. The First Lithium Fluorosilanolate–A Building Block for Directed Siloxane Synthesis (pages 678–679)

      Priv.-Doz. Dr. Uwe Klingebiel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106782

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      An example of the possible uses of the newly obtained, surprisingly stable title compound(1) is in the synthesis of the unsymmetric siloxane (2). At ca. 240°C (!) (1) forms the new, sterically very crowded cyclotrisiloxane (tBu2SiO)3.

    13. RuCo2(CO)11 and Ru2Co2(CO)13, Two New “Pure” Carbonylmetal Clusters (pages 679–680)

      Dipl.-Chem. Eckehart Roland and Prof. Dr. Heinrich Vahrenkamp

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106791

      The air-stable carbonyl-ruthenium-cobalt compound Ru, Co2(CO)13, prepared from the readily accessible, likewise novel cluster RuCo2(CO)11, contains a distorted Ru2Co2 tetrahedron with unsymmetrically distributed CO ligands. The polyhedron formed by the O atoms of the CO groups is the [13]-polyhe-dron of lowest energy. This is a further example illustrating that the structure of polynuclear carbonyl complexes depends on the spatial distribution of the ligands rather than on the localization of the bond relationships.

    14. Cluster-Construction: Synthesis and Structure of Fe2Co2(CO)11(PC6H5)2 and Fe2Co2(CO)11S2 (pages 680–681)

      Dipl.-Chem. Heinrich Vahrenkamp and Edward J. Wucherer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106801

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      A synthetic concept for the construction of tetranuclear clusters from two dinu-clear clusters exploits for the first time the finding that clusters are stabilized by ligand bridging [(la), E′ = PPhH, (1b). E′ = S (with S[BOND]S bonding); (2a), E = PPh, (2b), E = S].

    15. New Hydrophobic Protecting Groups for the Chemical Synthesis of Oligonucleotides (pages 681–683)

      Hans-Helmut Görtz and Prof. Dr. Hartmut Seliger

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106811

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      The selective separation of the 5′-hydroxy component from the product mixture obtained in the synthesis of polynucleotide fragments is rendered simple by use of 4-alkoxytrityl protecting groups with long alkyl chains. Thus, the compound (2) synthesized from (1), R = C16H3, and thymidine can be purified by chromatography on SiO2.

    16. Specific Separation of Products in Supported Oligonucleotide Syntheses Using the Triester Method (pages 683–684)

      Prof. Dr. Hartmut Seliger and Dr. Hans-Helmut Görtz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106831

      The mixture of homologous nucleotide fragments usually formed during carrier-oligonucleotide synthesis can be separated chromatographically so as to isolate the desired fragment, if the latter is protected at the 5′-end with a hexadecyloxytrityl group (see (2) in the previous communication).

    17. Catalytic Lithiation of 1-Olefins (pages 684–686)

      Prof. Dr. Borislav Bogdanović and Dr. Bernd Wermeckes

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106841

      Thumbnail image of graphical abstract

      Vinyllithium and higher trans-1-lithio-l-alkenes have been obtained in good yields by the reaction depicted below. Complexes of l,6,6aλ4-trithiapental-enes, lithium and e.g. ZnCl2 serve as catalysts.

    18. Isomer Formation in the Cycloaddition Reaction of 2,7-Dimethyl-2,4,6-octatriene with Tetracyanoethylene (pages 686–687)

      Dr. Alden D. Josey

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106861

      Thumbnail image of graphical abstract

      Contrary to earlier findings the octatriene (1) undergoes cycloaddition not only to give the Diels-Alder adduct (3), but also the [2 + 2]-adduct (2). There are plausible arguments for the mechanism of the reaction.

    19. Synthesis of a Novel Amphoteric Polyelectrolyte by Polymerization of 6-Amino-2,4-hexadienoic Acid in Layer Perovskites (page 687)

      Dr. Bernd Tieke and Prof. Dr. Gerhard Wegner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106871

      The topochemically controlled polymerization of 6-amino-2,4-hexadienoic acid in complexes with CdCl2, MnCl2 and FeCl2 is initiated by UV or 60Co-γ-radiation. Tacticity of the polymer, slight structural changes during transition from the monomer to polymer and control of reactivity by the type of ion in the matrix render the proposed course of reaction likely. The liberated amphoteric polyelectrolyte could be suitable as a polymeric complexing agent.

    20. A General Procedure for Intramolecular α-tert-Alkylation of Carbonyl Compounds (pages 687–689)

      Prof. Dr. Manfred T. Reetz, Dr. Ioannis Chatziiosifidis and Dipl.-Chem. Konrad Schwellnus

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106872

      Thumbnail image of graphical abstract

      Mono- and bicyclic as well as spirocyclic carbonyl compounds can be prepared by intramolecular tert-alkylation of olefins such as (1) with SnCl4. An O-stannyl derivative and a carbenium ion are probably intermediates in the reaction, which should find application in terpene and steroid syntheses.

    21. Preparation of Stable Diacyl Orthoester by O-Insertion on Reaction of a 1,2-Diketone with Lead Tetraacetate (pages 689–690)

      Dr. Siegfried Mohr

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106891

      Thumbnail image of graphical abstract

      Not the expected spirocyclic triketone but the diacyl orthoester (2) is formed on oxidative degradation of the amino acid function in (1) with Pb(OAc)4. The unusual stability of the orthoester is possibly due to the spatially overcrowded structure, evidenced by X-ray structure analysis.

    22. Trichloro(methyl)silane/Sodium Iodide, A New Regioselective Reagent for the Cleavage of Ethers (pages 690–691)

      Prof. Dr. George A. Olah, Altaf Husain, Dr. B. G. Balaram Gupta and Dr. Subhash C. Narang

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106901

      More than a dozen examples verify that ethers are cleaved regioselectively in very good yields by MeSiCl3/NaI in acetonitrile; primary and secondary methyl-, benzyl-, trityl- and tetrahydropyranyl ethers directly afford the primary and secondary alcohols. In the case of tert-alkylmethyl ethers only the tert-alkyl iodides are formed.

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    23. Synthesis of α-Trimethylsiloxythiolene and α,α′-Bis(trimethylsiloxy) Disulfides (pages 691–692)

      T. Aida, Prof. T.-H. Chan and Prof. David N. Harpp

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106911

      Thumbnail image of graphical abstract

      α-Trimethylsiloxythiols (1) have been synthesized in good yields for the first time–from aldehydes, H2S and (CH3)3SiCl in the presence of pyridine. The disulfides (2) were also obtained in good yields, by oxidation of (1) with MnO2. The thiols (1) can be added to olefins photochemically.

    24. Hexameric Molybdenum Tetrachloride (pages 692–693)

      Prof. Dr. Ulrich Müller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106921

      Thumbnail image of graphical abstract

      β-MoCl4 has a previously unobserved, unique structure: Cyclic hexamers are stacked on top of each other in layers. The stacking of the layers is disordered, but in such a way that the Cl atoms form a hexagonal closest packing.

    25. Gas Chromatographic Separation of Carbohydrate Enantiomers on a New Chiral Stationary Phase (pages 693–694)

      Prof. Dr. Wilfried A. König, Dipl.-Chem. Ingrid Benecke and Dr. Hagen Bretting

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106931

      The direct separation of simple, volatile derivatives of enantiomeric sugars has been achieved for the first time by glass-capillary gas chromatography of trifluoroacetyl derivatives on a temperature-stable, chiral stationary phase. The usefulness of the new method was demonstrated on an hydrolyzate of the galactan of the snail Helix pomatia.

    26. Reaction of Dibenzoyldiazomethane with 1-Diethylaminopropyne (pages 694–695)

      Dr. Rolf Huisgen, Dr. Maria Pilar Bosch Verderol, Dr. habil Alfred Gieren and Dipl.-Phys. Viktor Lamm

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106941

      Thumbnail image of graphical abstract

      The cycloaddition of the title compounds leads in the molar ratio 1 : 1 via the 3H-pyrazole (1) to the isomeric lH-pyrazole (2); this is accompanied by small amounts of a 1:2 adduct which, according to an X-ray structure analysis is the compound (3). (R = C6H5)

    27. The (η5-CH3C5H4)Mn(CO)2 Moiety as Protecting Group in the Monohalogenation of Diphenylsilane (pages 695–696)

      Priv.-Doz. Ulrich Schubert, Dipl.-Chem. Barbara Wörle and Ing. Peter Jandik

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106951

      Gram amounts of halosilanes Ph2Si(H)X, free of Si-containing side products, have been prepared by a protecting-group synthesis. In the initiating photochemical reaction only one Si[BOND]H bond is cleaved (R = η5-CH3C5H4).

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    28. Dispiro[2.0.2.4]deca-7,9-diene as a Ligand in Carbonyl-Transition Metal Complexes (pages 696–698)

      Dipl.-Chem. Dieter Wormsbächer, Dipl.-Chem. Frank Edelmann, Dr. Dieter Kaufmann, Dr. Ulrich Behrens and Prof. Dr. Armin de Meijere

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106961

      Thumbnail image of graphical abstract

      No opening of the three-membered ring takes place on reaction of a cyclohexadiene derivative containing a spirobicyclopropyl moiety with carbonyliron complexes. The stable cation-complex (1). X = BF4, can be synthesized by reaction of tricarbonyl(cyclohexadienyl)iron with HBF4.

    29. Direct and Inverse Reactivity-Selectivity Relationship in the [1.2]-Addition of Singlet Carbenes to Olefins (pages 698–699)

      Priv.-Doz. Dr. Wolfgang W. Schoeller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106981

      The selectivity of carbenes on addition to olefins can—contrary to common belief—increase with increasing reactivity. On the basis of the frontier orbital model two classes of carbenes can be differentiated: those with direct and those with inverse reactivity-selectivity relationship.

    30. 1H-Azepines from Anilides—A Novel Ring Expansion (pages 699–701)

      Dr. Heinz H. Eckhardt, Dorothea Hege, Dr. Werner Massa, Prof. Dr. Hartwig Perst and Roland Schmidt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198106991

      Thumbnail image of graphical abstract

      A new route to the 1H-azepines (2) starts from the anilides (1). It leads via benzenium ions—and in the case of X = R1CO via oxazolines—to (2).

  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 702)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198107021

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