Angewandte Chemie International Edition in English

Cover image for Vol. 18 Issue 5

May 1979

Volume 18, Issue 5

Pages 337–420

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 5/1979)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197903371

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 5/1979)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197903372

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Permeability of the Outer Membrane of Bacteria (pages 337–350)

      Prof. Dr. Hiroshi Nikaido

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197903373

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      Structure-function relations of biological membranes can be studied on the outer membrane of Gram-negative bacteria. Use of mutants showed, e.g., that small hydrophilic molecules pass through the membrane in a different manner from small hydrophobic molecules.

    2. A Model of Simple Liquids (pages 350–363)

      Prof. Dr. Werner A. P. Luck

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197903501

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      The chemist is concerned mainly with liquids; a comprehensible hole model has proved a remarkably powerful tool in furthering our understanding of liquid properties and in providing quantative estimates.

    3. Circular Dichroism and Absolute Conformation: Application of Qualitative MO Theory to Chiroptical Phenomena (pages 363–377)

      Prof. Dr. Günther Snatzke

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197903631

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      The gap separating theory and empiricism of CD analysis can be at least partly bridged by use of “qualitative MO theory”. The aim is to obtain rules predicting the relationship between molecular geometry and the sign of CD.

    4. A Basis for Orbital Symmetry Rules (pages 377–392)

      Prof. Dr. John Ross, Prof. Dr. George M. Whitesides and Prof. Dr. Horia Metiu

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197903771

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      In order to qualify and extend the Woodward-Hoffmann rules, the effect of molecular symetry on the rate of chemical reactions is examined by an approach differing from that employed previously. The reactions are regarded as electronic transitions between reactant and product states, with the states being described as quasiadiabatic potential energy surfaces. This unorthodox apporach also permits a distinction to be made between concerted and non-concerted reactions.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Catalytic Conversion of Aldehydes into Higher α-Siloxy Aldehydes by Hydrosilane and Carbon Monoxide (pages 393–394)

      Prof. Dr. Shinji Murai, Toshikazu Kato, Prof. Dr. Noboru Sonoda, Dr. Yoshio Seki and Prof. Dr. Kazuaki Kawamoto

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197903931

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      Chain lengthening and functionalization of aldehydes–leaving the aldehyde group intact–are possible with the aid of the reaction shown below. The products (2) are useful intermediates which are otherwise difficult to prepare.

    2. Synthesis of Thymosin α1, a Polypeptide of the Thymus (pages 394–395)

      Priv.-Doz. Dr. Christian Birr and Dipl.-Chem. Ulrich Stollenwerk

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197903941

      Polypeptides from the thymus are being studied with regard to their immunological function. Synthesis of the strongly acidic peptide thymosin α1, made up of 28 amino acids, in biologically active from enhances its potential use in research and–possibly–in therapy.

    3. Mesityl(diphenylmethylene)arsane (pages 395–396)

      Dr. Theo C. Klebach, Dr. Hans van Dongen and Prof. Dr. Friedrich Bickelhaupt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197903951

      A localized As[DOUBLE BOND]C double bond bearing three aryl groups is found in the new compound (1). This compound adds even traces of water to give (2), the reaction occurring faster than air oxidation.

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    4. Carbene-Carbene Rearragements of cis-and trans-2-(1,3-Butadienyl)cyclopropylidene (pages 396–397)

      Dr. Udo H. Brinker and Dipl.-Chem. Ilona Fleischhauer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197903961

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      The configurationally isomeric carbenes(1) and (2)–the first such pair obtained–behave with remarkable regiospecificity in carbene-carbene rearrangements. The 1,5-C shifts (2) [RIGHTWARDS ARROW] (3) is new.

    5. Asymmetric Synthesis of Ant Alarm Pheromones—α-Alkylation of Acyclic Ketones with almost Complete Asymmetric Induction (pages 397–399)

      Dr. Dieter Enders and Dipl.-Chem. Herbert Eichenauer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197903971

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      The chiral ant alarm pheromone(S)-(3) and many similar ketones have been synthesized as the almost pure enantiomers from achiral precursors such as (1). After lithiation, the hydrozone (S)-(2) is treated with n-C3H7I; the resulting hydrazone is cleaved to give the α-alkylated ketone (S)-(3).

    6. A Metalated Allylurea with Sterically protected Carbonyl Grourp as Novel d3-Reagent (pages 399–400)

      Dipl.-Chem. Tillmann Hassel and Prof. Dr. Dieter Seebach

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197903991

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      Exclusive reaction at the γ-position relative to nitrogen takes place between the urea derivative (2), M = MgBr, and electrophiles. The new reagent is readily prepared from (1) and MgBr2·ether and corresponds to a “propionaldehyde-homoenolate synthon”.2, M = Li, froms α- and γ-substituted products.

    7. Ligand Concentration-Control in the system Nickel(0)/Triphenylphosphane/Butadiene (pages 400–401)

      Ing. (grad.) Frank Brille, Prof. Dr. Paul Heimbach, Dipl.-Chem. Joachim Kluth and Dr. Hartmut Schenkluhn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904001

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      In order to elucidate the catalytic steps in the Ni0/PPh3 (=L)/butadiene system, a control map was plotted (see right). To this end, the proportion of butadiene oligomers (1)(5) was determined as a function of [L]0/[Ni]0 (abscissa: lg[L]0/[Ni]0).

    8. Separation of Steric and Electronic Effects in the Reaction Enthalpies of Association of Phosphorus Ligands (pages 401–402)

      Dr. Hartmut Schenkluhn, Ing. (grad.) Walter Scheidt, Dr. Bruno Weimann and Ing. (grad.) Manfred Zähres

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904011

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      An understanding of the directing influence of Lewis bases in homogeneous transition metal catalysis is brought nearer by data characterizing the metal-ligand bond. The enthalpy of reaction of (1) with L was measured for 22 phosphorus ligands L and resolved into “steric” and “electronic” components.

    9. Regiospecific Synthesis of Disubstituted Benzene Derivatives (pages 402–404)

      Dr. Guy Félix, Dr. Jacques Dunoguès and Prof. Dr. Raymond Calas

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904021

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      Stepwise replacement of the Me3Si groups of readily accessible ortho-, meta-, or para-(1), combined with modification of the newly introduced groups, permits the synthesis of a variety of disubstituted benzene derivatives. The directing effect of the first substituent upon the second one no longer applies.

    10. Unsymmetrical Binuclear Complexes of Tungsten with Three OR Bridges, η3-C7H7(CO)2W(OR)3W(CO)24-C7H8 (page 404)

      Dipl.-Chem. Wolfgang Schulze, Dr. Klaus Weidenhammer and Prof. Dr. Manfred L. Ziegler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904041

      No analogy between molybdenum and tungsten is observed in the reaction of η7-C7H7M(CO)2X (1) with NaOR: (1), M = Mo, forms the paramagnetic compound (2) with two Mo centers in different oxidation states. In the case of (1), M = W, however, a C7H7 ligand is surprisingly reduced to C7H8 by H; the 18-electron rule applies to both W atoms in (3).

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    11. β-Stannylated Ynamines as Aminoethylation Reagents (pages 405–406)

      Dr. Gerhard Himbert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904051

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      Introduction of a R2N[BOND]C[TRIPLE BOND]C group, e.g. into acyl chlorides and imidoyl chlorides, is possible with the reagent (1). The reactive CC linked C2 unit in the product permits further reactions.

    12. Discovery of an Exceptionally Long Unbridged Carbon-Carbon Bond (pages 406–407)

      Dr. Walter Littke and Dr. Ulrich Drück

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904061

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      The bond length of 1.638 Å found for the central C[BOND]C bond of 5,6-dibutyl-5,6-diphenyldecane (1) is a record for unbridged systems. The thermolabile hydrocarbon exhibits numerous H/H contacts, some of which are very close.

    13. Regio- and Stereospecific Hydroxylation of Alicyclic Hydrocarbons with Substituted Perbenzoic Acids (pages 407–408)

      Dipl.-Chem. Walter Müller and Prof. Dr. Hans-Jörg Schneider

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904071

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      Reactions of the type RH [RIGHTWARDS ARROW] ROH rarely yield homogeneous products. However, substituted perbenzoic acids transform the cyclic “paraffins” cis-and trans-(1) to (3), X = H, regio- and stereospecifically into the corresponding compounds with X = OH. Acyclic alkanes are likewise oxidizable.

    14. Problem of the Structure of Carbodiphosphoranes, R3PCPR3: New Aspects (pages 408–409)

      Prof. Dr. Hubert Schmidbaur, Dr. Georg Hasslberger, Ulrich Deschler, Dr. Ulrich Schubert, Dr. Charles kappenstein and Dr. Albin Frank

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904081

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      The PCP angle in crystalline carbodiphosphoranes and the triboluminescence shown by some modifications, e.g. of Ph3PCPPH3 have been thought to be related for some time. The search for further outstanding structural features has now led to a deeper understanding of this phenomenon and also showed that the bonding in MePh2PCPPh2Me is far better explained in terms of the polar (A) than by the nonpolar from (B).

    15. Cyclobutadiene-Metal Complexes as Potential Intermediates in Alkyne Metathesis: Flash Vacuum Pyrolysis of Substituted η4-Cyclobutadiene-η5-cyclopentadienyl-cobalt Complexes (pages 409–411)

      John R. Fritch and Prof. Dr. K. Peter C. Vollhardt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904091

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      The mechanism of alkyne methathesis is still a matter of controversy. Flash thermolysis of some selected complexes (1) shows them to be conceivable intermediates, being able to form transient bis(alkyne)cobalt complexes in the gas phase; after rotation they recyclize or decompose with liberation of alkynes.

    16. 1,2,4,5-Tetrahydrodicyclobuta[b,e]pyridine (page 411)

      Alaric Naiman and Prof. Dr. K. Peter C. Vollhardt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904111

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      The most strongly strongly strained pyridine derivative, the tricyclic compound (2), has been synthesized by flash pyrolysis. (2) still seems to possess typical “aromatic” properties.

    17. Cyanohalophosphates(III)—Hypervalent Anions Containing λ5-Phosphorus(III) (pages 411–412)

      Prof. Dr. Alfred Schmidpeter and Dipl.-Chem. Franz Zwaschka

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904112

      Hypervalent phosphorus(III) compounds (having four ligands and a lone pair on the phosphorus) are poorly characterized. The crystalline crown-ether-stabilized salts (1) and (2) have now been isolated.

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    18. 1H-1,2,3, σ2-Diazaphospholes — Bond Delocalization in σ2-Phospholes (pages 412–413)

      Dr. Josef Helmut Weinmaier, Dr. Jörg Luber, Prof. Dr. Alfred Schmidpeter and Dr. Siegfried Pohl

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904121

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      The isomeric 1H- and 2H-diazaphospholes(1) and (2)—formally an imino- and a methylenephosphane—should be distinguishable chemically and physically. (2) is known; isolation and structural elucidation of (1) permitted the first comparison: Cyclic 6π delocalization is about as extensive as in the five-membered ring heterocycles with [BOND]CH[DOUBLE BOND] in place of [BOND]P[DOUBLE BOND].

    19. syn-Anthracene 4a,10:9,9a-Dioxide (pages 413–415)

      Prof. Jean Rigaudy, Albert Defoin and Joële Baranne-Lafont

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904131

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      The rearrangement of an epidioxide to a compound with two epoxide groups known to occur with cycloalkienes and substituted arenes–has now accomplished with unsubstituted (1) by prolonged irradiation (λ > 435 nm). (2) is the thermolabile primary product of thermal isomerization of (1).

    20. SN Ring with Di-, Tri-, and Tetra-Coordinated Sulfur Atoms by Nucleophilic Substitution (page 415)

      Prof. Dr. Herbert W. Roesky, Dipl.-Chem. Michael Witt, Prof. Dr. Bernt Krebs and Dipl.-Chem. Hans Jürgen Korte

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904151

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      Nucleophilic substitutions of sulfur-nitrogen compounds were previously unknown. Meanwhile, the surprisingly stable salt (2) has been obtained quantitatively from (1) and NaOCH3; its S atoms exhibit three different coordination numbers.

    21. (−)579-Bis[(S)-(+)-O,O′(1,1′-binaphthly-2,2′-diyl)-dithiophosphato]nickel(II) — The First Dithiophosphato Complex to Have Axial Chirality (pages 415–416)

      Dipl.-Chem. Ernst W. Hoffmann, Prof. Dr. Wilhelm Kuchen, Wolfgang Poll and Dr. Hartmut Wunderlich

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904152

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      The optically active NiII complex(1) could be prepared from the (+)-methyl benzylammonium salt of the (+)-acid (2) and nickel acetate. Metal complexes of dithiophosphoric and dithiphosphinic acids are of interest, e.g., adsorbents for chromatographic separation of Lewis bases.

    22. Structural Isomers of Palladium Complexes of Type C5H5Pd(2-RC3H4)L — A Case of Simultaneous π/σ and σ/π Rearrangement of Two Organic Ligands (pages 416–417)

      Prof. Dr. Helmut Werner and Dr. Alfred Kühn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904161

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      Interesting structural features of palladium complexes have been observed for (1): in solution (1a) undergoes very fast metallotropic rearrangement, i.e. it has a fluxional structure, whereas two bond isomers interconvert in the case of the homologous compound (1b).

    23. Catalysis of Hydrogen Formation from an Organic Radical in Aqueous Solutions by Colloidal Silver (page 418)

      Prof. Dr. Arnim Henglein

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904181

      Short-lived radicals such as (1) can be compelled to undergo unusual reactions if they are generated in the presence of a metal colloid catalyst in aqueous solution. Instead of combining, disprotionating, or dismuting, the radicals (1) participate in a redox process leading to evolution of H2, according to the overall equation:

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  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Book Review: Surfactants and Interfacial Phenomena. By M. J. Rosen (page 419)

      M. J. Schwuger

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904192

    2. Book Review: Transform Techinques in Chemistry. Edited by P. R. Griffiths (page 420)

      R. R. Ernst

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904201

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