Angewandte Chemie International Edition in English

Cover image for Vol. 18 Issue 6

June 1979

Volume 18, Issue 6

Pages 421–492

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 6/1979)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904211

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 6/1979)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904212

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    1. Triphase Catalysis [New synthetic methods (27)] (pages 421–429)

      Prof. Steven L. Regen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904213

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      The advantages of heterogeneous catalysis and phase transfer catalysis are combined in triphase catalysis (TC). In this novel method the catalyst, substrate, and reagent are present in separate phases. An example of the TC reaction is the Br/CN exchange in presence of the solid catalyst (1).

    2. Key Building Blocks of Natural Product Biosynthesis and Their Significance in Chemistry and Medicine (pages 429–439)

      Prof. Dr. Burchard Franck

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904291

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      Large groups of natural products originate from the same biosynthetic precursor—the key building block. Examples are D-glucose, shikimic acid, acetic acid, and amino acids. The conversion of key building blocks into natural products serves as a model for the development of more efficient syntheses in chemistry.

    3. Photochemical Reactions of Surfactant Molecules in Condensed Monolayer Assemblies—Environmental Control and Modification of Reactivity (pages 440–450)

      Professor Dr. David G. Whitten

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904401

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      The effects of a controlled microenvironment on reactivity have been investigated on compounds containing surface active and photoreactive groups in the same molecule. Substantial environmental effects have been observed, inter alia, in the cis-trans isomerization of olefins, in ketone photoeliminations, and in ligand exchange and photoredox reactions.

    4. The Chemistry of Isolated Cations (pages 451–461)

      Dr. Richard D. Bowen, Dr. Dudley H. Williams and Prof. Dr. Helmut Schwarz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904511

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      Metastable peaks observed in mass spectra—previously regarded in some quarters as a nuisance—contain valuable information on the gas-phase chemistry of ions. They are known to arise from the dissociation of ions after acceleration.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    1. An Easily Prepared, Air-Stable Compound with a Triple Metal-to-Metal (MoMo) Bond (pages 462–463)

      Dr. Avi Bino and Prof. Dr. F. Albert Cotton

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904621

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      A “simple” fourfold bridged Mo[TRIPLE BOND]Mo triple bond is present in the purple-red complex (1) which is formed by slow mixing of the reactants listed below. “Simple” M[TRIPLE BOND]M bonds do not contain δ bonding (σ4 π4).

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    2. Transition Metal Complexes with the Tetrathiosquarate Dianion as Bridging Bischelate Ligand (pages 463–464)

      Dipl.-Chem. Franz Götzfried, Prof. Dr. Wolfgang Beck, Dr. Anton Lerf and Angelika Sebald

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904631

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      Organometallic compounds having a chain-type structure such as (1) are of interest as potential one-dimensional electrical conductors. An example of (1) is Ni25(C4S4)26K2·x H2O (x ≈ 8); the conductivity of the compressed powder at 20 °C is 5 × 10−4 Ω−1 cm−1. The monomeric complex (2) can be reduced irreversibly in two steps by voltammetry.

    3. Ag10Si4O13—The First Tetrasilicate (page 464)

      Dr. habil. Martin Jansen and Dr. Hans-Lothar Keller

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904641

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      A new chain-like silicate oligo-anion, the first tetrasilicate, has been synthesized as the vermilion silver salt by reaction of Ag2O with SiO2 (low-temperature quartz) under enhanced oxygen pressure at 500–600°C. An X-ray structure analysis has been performed.

    4. Chemical Synthesis of Human Blood Group B Antigenic Determinant: Type 2 Tetrasaccharide (pages 464–465)

      Marie-Louise Milat and Prof. Dr. Pierre Sinaÿ

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904642

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      The blood group substances in the AB0 system contain carbohydrate chains which determine, e.g. the compatibility of the blood of donor and recipient on transfusion. The terminal tetrasaccharide (type 2) of substance B has now been synthesized via the “imidate route”.

    5. Facile, Highly Selective Synthesis of α- and β-Disaccharides from 1-O-Metalated D-Ribofuranoses (pages 466–467)

      Prof. Dr. Richard R. Schmidt and Dipl.-Chem. Manfred Reichrath

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904661

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      α- and β-Disaccharide syntheses not requiring halogenoses and heavy metals have many advantages. Depending on the nature and size of the 5-O-substituent R, compound (1) is metalated to give (2) (R [DOUBLE BOND] H) or (3) (R [DOUBLE BOND] CPh3, tBuMe2Si); (2) is a precursor of β-, and (3) a precursor of α-disaccharides

    6. A New Synthesis of Fulminic Acid (pages 467–468)

      Prof. Dr. Curt Wentrup, Bernd Gerecht and Horst Briehl

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904671

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      A safe synthesis of fulminic acid(3) has been accomplished by flash pyrolysis of the oxime (1) or (2). In contrast to earlier syntheses, this method avoids the use of highly explosive metal fulminates.

    7. Polycyclic Azoalkanes via Dipolar Cycloaddition of 4-Phenyl-1,2,4-triazoline-3,5-dione with Strained Bicyclic Olefins (pages 468–469)

      Prof. Dr. Waldemar Adam, Dr. Ottorino De Lucchi and Dr. Ihsan Erden

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904681

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      Polycyclic hydrocarbons containing the [BOND]N[DOUBLE BOND]N[BOND] structural unit are of interest as precursors of diradicals. (1) and similar compounds can be conveniently prepared by the unusual cycloaddition shown below.

    8. tetrahedro-Tetraphosphorus as Monodentate Ligand in a Nickel(0) Complex (page 469)

      Dr. Paolo Dapporto, Dr. Stefano Midollini and Prof. Dr. Luigi Sacconi

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904691

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      An intact P4 molecule is coordinated as η1 ligand to Ni0 in complex (2). X-ray structure analysis reveals that the nickel atom is in an approximately tetrahedral environment of three phosphorus atoms of the additional ligand “np3” and one phosphorus atom of the P4 unit.

    9. Stepwise Reaction of Phenylbis(trimethylsilyl)phosphane with Phosgene—Isolation of a (Phosphinomethylene)phosphane (pages 469–470)

      Prof. Dr. Rolf Appel and Dipl.-Chem. Volker Barth

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904692

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      Three intermediates of chlorination of PhP(SiMe3)2 with phosgene have been isolated and some of them characterized. The open-chain compound (2) having a P[DOUBLE BOND]C bond deserves special mention.

    10. Bicyclo[2.2.2]octa-5,7-diene-2-carboxylic Acid and 7-Methylenebicyclo[2.2.2]octa-2,5-diene (pages 470–471)

      Prof. Dr. Rudolf Gompper and Dipl.-Chem. Karl-Heinz Etzbach

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904701

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      7-Substituted bicyclo[2.2.2]octadienes such as (1) and (2) are of interest, e.g. as precursors of the potentially antiaromatic anion of (3) and its dibenzo analog (4). Compound (1) is obtainable from dihydrophthalic acid and methyl acrylate (Diels-Alder reaction, electrolysis, hydrolysis).

    11. Structure and Formation of Triorganylphosphoniocyclopropenylium Ions (pages 472–473)

      Doz. Dr. Robert Weiss, Dr. Claus Priesner and Dipl.-Chem. Hilmar Wolf

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904721

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      The first cation to have a hetero[3]radialene resonance structure is present in the salt (1). Its formation can be rationalized in terms of an elimination/addition reaction proceeding via a nucleophilic carbene. Such reactions were hither-to unknown in the Cmath image system.

    12. Synthesis of a Donor-Substituted Tris(cyclopropenylio)cyclopropenylium Salt (pages 473–474)

      Doz. Dr. Robert Weiss, Dipl.-Chem. Marion Hertel and Dipl.-Chem. Hilmar Wolf

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904731

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      The first tetracarbenium ion has now been synthesized as the tetraperchlorate (3) from the likewise new silyl-substituted Cmath image compound (1). The experimental findings suggest the intermediacy of the free nucleophilic carbene (2) (R [DOUBLE BOND] isopropyl).

    13. New Synthesis of Amino Acids from Halogenated Carboxylic Esters (pages 474–476)

      Prof. Dr. Franz Effenberger and Dr. Karlheinz Drauz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904741

      Chemically synthesized α-amino acids are used to fortify foodstuffs and animal feeds. The drawbacks of former syntheses are avoided in the reaction sequence (1)[RIGHTWARDS ARROW](2)[RIGHTWARDS ARROW](3) which leads, e.g. to lysine in an overall yield of 52% (X [DOUBLE BOND] Cl, Br; R1 [DOUBLE BOND] Me, Et; M [DOUBLE BOND] K, Na, Li)

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    14. The Sequences of the Membrane-Modifying Peptide Antibiotic Trichotoxin A-40 (pages 476–477)

      Dipl.-Chem. Hans Brückner, Prof. Dr. Wilfried A. König, Dipl.-Chem. Michael Greiner and Prof. Dr. Günther Jung

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904761

      A possible model for nerve conduction is provided by the peptide antibiotic trichotoxin A-40. The first complete sequence determination was accomplished once it had been recognized that the peptide can be fragmented highly selectively with anhydrous trifluoroacetic acid. The high content of aminoisobutyric acid (Aib) is remarkable.

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    15. Titanocene Dichloride—The First Metallocene with Cancerostatic Activity (pages 477–478)

      Prof. Dr. Hartmut Köpf and Dr. Petra Köpf-Maier

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904771

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      The cancerostatic activity of metal complexes can be tested on mice by injection of tumor cells and, 24 h later, the substance to be investigated. Compound (1), selected partly because of its structural similarity to the antitumor agent (2), exhibited a cure rate of over 80% in the therapeutic range.

    16. Thermal Generation of Pteridines and Flavines from Amino Acid Mixtures (pages 478–483)

      Dipl.-Chem. Bettina Heinz, Prof. Dr. Walter Ried and Prof. Dr. Klaus Dose

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904781

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      Pteridines and flavines could have arisen under prebiotic conditions from amino acids and the compounds allophanic acid, guanidinoformic acid, biuret, and formamidine obtainable from NH3, CO2, and H2O. This concept is supported by the detection of compounds such as (1) in thermolyzed mixtures of amino acids.

    17. [2 + 4]-Cycloadditions with Di-tert-butyl Acetylenedicarboxylate (pages 483–484)

      Gisela Weber, Dr. Klaus Menke and Prof. Dr. Henning Hopf

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904831

      Di-tert-butyl acetylenedicarboxylate is a valuable cycloaddition reagent—as has been confirmed for several examples. However, it is not quite so new as was stated on p. 149 of the February issue of this Journal. The first synthesis was published slightly earlier by Hopf et al. in Chemische Berichte.

    18. Methylidynetris(dimethylphosphane) (page 484)

      Dr. Hans Heinz Karsch, Dr. Ulrich Schubert and Dietmar Neugebauer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904841

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      Stabilization of a negatively charged C atom by three PMe3 ligands proves so successful that the resulting compound (4) is stable towards air, water, and even trifluoroacetic acid, decomposing only at about 330 °C. According to X-ray analysis, [C(PMe3)3]2+ is trigonal-planar. The ylide (4) has also been synthesized from the likewise new trisphosphane (3) via the lithium salt [analogous to (1) [RIGHTWARDS ARROW] (2)] and its reaction with MeI.

    19. A Phosphorus Ylide with Symmetrical Resonance-Stabilized sp2-Carbanion (pages 484–485)

      Dr. Hans Heinz Karsch, Dipl.-Chem. Beate Zimmer-Gasser, Dietmar Neugebauer and Dr. Ulrich Schubert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904842

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      Stabilization of a negatively charged C atom by three PMe3 ligands proves so successful that the resulting compound (4) is stable towards air, water, and even trifluoroacetic acid, decomposing only at about 330 °C. According to X-ray analysis, [C(PMe3)3]2+ is trigonal-planar. The ylide (4) has also been synthesized from the likewise new trisphosphane (3) via the lithium salt [analogous to (1) [RIGHTWARDS ARROW] (2)] and its reaction with MeI.

    20. Asymmetric Epoxidation of Simple Olefins with an Optically Active Molybdenum(VI) Peroxo Complex (pages 485–486)

      Prof. Dr. Henri B. Kagan, Dr. Hubert Mimoun, Dipl.-Chem. Christoph Mark and Prof. Dr. Volker Schurig

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904851

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      Asymmetric syntheses of non-functionalized oxiranes can be accomplished with the aid of the new optically active MoVI peroxo complex (1). Thus e. g., propene, 1-butene, and 3-methyl-1-butene were epoxidized to the corresponding R-oxirane in ca. 29, 31, and 16% optical yield (enantiomeric excess). Previously, only activated olefins (styrenes, allyl alcohols, etc.) could be epoxidized asymmetrically.

    21. Krypton and Xenon Inclusion Compounds of Complex Metal Cyanides (pages 486–487)

      Dr. Manfred Kämper, Dipl.-Chem. Madlon Wagner and Prof. Dr. Armin Weiss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904861

      The inclusion of noble gases in host latticese.g. CdPt(CN)6 takes up 1.046 Kr or 1.128 Xe per formula unit if the crystals are grown in the presence of the gas (64 bar)—corresponds to a compression (⩾118 bar). However, CdPt(CN)6 is too expensive for industrial use. The cavities of the cage structure surprisingly remain vacant on crystallization from water.

    22. A New Lithium-Nickel Polynuclear Complex: Ni(C12H17NiLi)2(THF)4 (pages 487–488)

      Dr. Klaus Jonas, Priv.-Doz. Dr. Carl Krüger and Dr. Janine C. Sekutowski

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904871

      Three linearly arranged nickel atoms and two coordinatively unsaturated Li and two pentacoordinated C atoms present in the new complex (2) (C12H18 = all-cis-1,5,9-cyclododecatriene). Compound (2), formed as by-product in the lithiation of C11H18Ni0, was obtained from (1) in 30% yield.

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    23. Nickel(0)-Induced Synthesis of Ethyllithium from Lithium, Hydrogen, and Ethylene (pages 488–489)

      Dr. Klaus Jonas and Dr. Klaus Richard Pörschke

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904881

      Lithium-nickel(0) system often prove surprising: thus (COD)2Ni and Li react together in tetrahydrofuran to give (COD)2NiLi2(THF)4, which can be reduced by H2 under normal pressure to form the new “lithium hydride” (1). Unlike LiH, (1) adds to C[DOUBLE BOND]C double bonds; it forms C2H5Li with ethylene.

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    24. Metalation of Pyrans and Dihydropyridines: When is an 8 π-System Cost Effective? (pages 489–490)

      Prof. Dr. Manfred Schlosser and Dipl.-Chem. Philippe Schneider

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904891

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      An organometallic 8 π system(2) could be generated by reaction of (1) with trimethylsilylmethylpotassium. The intermediate (2) is moderately stable at −50°C and reacts with MeI to give (3) and (4). E [DOUBLE BOND] Me (1:1), and with Me3SiCl to give (4), E [DOUBLE BOND] Me3Si.

  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
      Erratum (page 492)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197904922

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