Angewandte Chemie International Edition in English

Cover image for Vol. 23 Issue 6

June 1984

Volume 23, Issue 6

Pages 395–466

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 6/1984)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198403951

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      The cover shows schematically the structure of the d1, -domain of lactate dehydrogenase in the native state. In NAD-dependent dehydrogenases, many amino acids can be exchanged without causing a drastic change in the tertiary structure (“degenerate folding code”). Furthermore, only a limited number of amino acids appear to exist which form a well-defined, stable tertiary structure. These two discoveries provide an explanation for the surprisingly small number of “folding topologies” which are found in the greater number of known structures.—For more information see the article by R. Jaenicke on page 395ff.

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 6/1984)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198403952

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Protein Folding and Protein Association (pages 395–413)

      Prof. Dr. Rainer Jaenicke

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198403953

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      Two information codes apparently exist on the pathway from the gene to the functional product of its expression: the well-known genetic code and the “code of protein folding”. In contrast to the genetic code, the folding code is shrouded in obscurity. Certain is that the folding occurs spontaneously and autonomously. This rapid process can be fully simulated in vitro.

    2. Synthesis of Anti-Inflammatory α-Arylalkanoic Acids by 1,2-Aryl Shift. New Synthetic Methods (42) (pages 413–419)

      Dr. Claudio Giordano, Dr. Graziano Castaldi and Dr. Fulvio Uggeri

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404131

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      A convenient route to the important pharmaca of type 2 is opened up—also on the industrial scale—by the reaction 1 [RIGHTWARDS ARROW] 2; X = halogen, tosyl, or diazo. As an example of a tried and tested, anti-inflammatory α-arylalkanoic acid, Ibuprofen 3 may be mentioned.

    3. Pyrylium Mediated Transformations of Primary Amino Groups into Other Functional Groups. New Synthetic Methods (41) (pages 420–429)

      Prof. Dr. Alan R. Katritzky and Dr. Charles M. Marson

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404201

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      Exchange of the amino by a nucleophilic group—tantamount to the reaction R[BOND]NH2 [RIGHTWARDS ARROW] R[BOND]Nu—is facilitated as shown below. Both steps can be carried out using a variety of amines under mild conditions; in this way, even selective reactions can be performed in the presence of many functional groups.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Synthesis of 3-Deoxy-D-manno-2-octulosonic Acid (KDO) (pages 430–431)

      Prof. Dr. Richard R. Schmidt and Rainer Betz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404301

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      KDO, an integral component of the lipopolysaccharides of gram-negative bacteria, can be prepared by a route analogous to its biosynthesis. The key step of this novel approach to the ammonium salt of KDO, 1, is the reaction of a C-lithiated, functionally substituted acrylic acid (C3-building block) with a D-arbinose derivative (C5-building block)

    2. Ambidentate Behavior of Mononuclear Vinylidenerhodium Complexes—Novel C[BOND]C Coupling of a Methyl to a Vinylidene Group (pages 431–432)

      Prof. Dr. Helmut Werner, Justin Wolf, Dr. Gerhard Müller and Prof. Dr. Carl Krüger

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404311

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      The mononuclear species 2 ([Rh][DOUBLE BOND]C5H5(iPr3P)Rh, R[DOUBLE BOND]H) can be regarded as a “metallaallene” having numerous coordination possibilities. In 3 the C[DOUBLE BOND]CH2 group bridges a hetero metal-metal bond, and in 1, 2 is bonded to Rh like an alkene or alkyne.

    3. Ring-Opening of Methylene-Bridged Dimetal Complexes by Bases (pages 432–434)

      Prof. Dr. Wilhelm Keim, Dr. Michael Röper, Dr. Heinz Strutz and Prof. Dr. Carl Krüger

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404321

      For the mechanistic explanation of the Fischer-Tropsch synthesis, model reactions at dimetallacyclopropane complexes such as 1 are of considerable interest. Base-induced, ring-opening has now been achieved for the first time. In this way, methylene bridges react with coordinated CO to afford the salt 2, which was isolated and fully characterized.

      • equation image
    4. Structure of a Novel μ3-Oxo-Femath imageCrIII-Glycine Complex (pages 434–435)

      Dr. William Clegg, O. Mi Lam and Dr. Brian P. Straughan

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404341

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      Notable structural features are exhibited by the title compound, a heterometal analogue of a μ3-oxo-Femath image alanine complex which has been discussed as a model for the iron containing “core” of ferritin. In the crystal, The Fe2Cr-triangles are ordered; the structure is similar to that of the Fe3-analogue; peripheral ligands and counterions have only a slight influence on the structure.

    5. Asymmetric Hydrogenation of α-(Acetylamino)cinnamic Acid with a Novel Rhodium Complex; the Design of an Optimal Ligand (pages 435–436)

      Dr. Ulrich Nagel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404351

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      A novel, chiral bisphosphane ligand with variable N-substituents is contained in the Rh complex 1. 1 (BF4 salt) catalyzes the hydrogenation of α-(acetylamino)cinnamic acid, even at high H2-pressure and with large amounts of substrate, in up to 99% ee. 1 is also highly propitious when bonded to carriers.

    6. The Allyloxycarbonyl (Aloc) Moiety—Conversion of an Unsuitable into a Valuable Amino Protecting Group for Peptide Synthesis (pages 436–437)

      Prof. Dr. Horst Kunz and Carlo Unverzagt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404361

      A novel method for the cleavage of the Aloc protecting group (Aloc = allyloxycarbonyl) permits the effective and selective synthesis of sensitive peptide derivatives, e.g. with serine residues. The protecting group can be removed from peptide esters such as Aloc-Phe-Ser(tBu)-OtBu via catalytic allyl transfer with [Pd(PPh3)4] to dimendone; the tBu groups are retained. In contrast, with CF3COOH only the tBu groups are removed from the Aloc-tBu esters.

    7. Transfer of Chirality in the Addition of Chiral α-Chloroallylboronate Esters to Aldehydes (pages 437–438)

      Prof. Dr. Reinhard W. Hoffmann and Dipl.-Chem. Bernd Landmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404371

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      The chiral integrity of an auxiliary reagent must be transferred to the new center of chirality in every enantioselective synthesis. This is achieved particularly effectively if the controlling center, as in 1, directly influences the conformation of a cyclic transition state.

    8. Ligand Extrusion from the As4S4-Cage by [C5Me5(CO)2Mo]2: Formation of (C5Me5)2Mo2(CO)4(μ,η2-As2), C5Me5(CO)2Mo(η3-As3), and (C5Me5)2Mo2As2S3 (pages 438–439)

      Prof. Dr. Ivan Bernal, Prof. Dr. Henri Brunner, Walter Meier, Heike Pfisterer, Dr. Joachim Wachter and Prof. Dr. Manfred L. Ziegler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404381

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      Three unusual complexes—inter alia the first complex with an As[BOND]S ligand and a monosubstituted derivative of yellow arsenic—were obtained via the previously unknown title reaction of realgar.

    9. Thiopenam Derivatives from Alkynyl Silyl Sulfides and 4,5-Dihydrothiazoles (pages 439–440)

      Prof. Dr. Ernst Schaumann, Dr. Wolf-Rüdiger Förster and Dr. Gunadi Adiwidjaja

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404391

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      Replacement of the oxo group on the four-membered ring of penicillin and other β-lactam antibiotics by sulfur proceeds in extremely low yields. Thiopenam derivatives of this type can now be synthesized via cycloaddition and desilylation (R1= tBu, R2 = H, CO2Me, R3 = H, Me)

    10. A Photochemical Entry to Macrocyclic Mono- and Dilactones (pages 440–442)

      Prof. Dr. Gerhard Quinkert, Dr. Gerd Fischer, Dipl.-Chem. Uta-Maria Billhardt, Dipl.-Chem. Jürgen Glenneberg, Dipl.-Chem. Ulrich Hertz, Dr. Gerd Dürner, Dr. Erich F. Paulus and Dr. Jan W. Bats

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404401

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      The activation of dienylketenes 2 with diazabicyclooctane can lead—with appropriate substitution—to monolactones 3 or di- (and tri-)lactones. The educt rac-1, R = CH3, X = H, n = 9, affords 3 in ca. 30% yield.

    11. Adducts of the Ketene (1E,3Z)-1,2,3,4,5-Pentamethyl-6-oxo-1,3,5-hexatrienyl Acetate (pages 442–444)

      Prof. Dr. Gerhard Quinkert, Dipl.-Chem. Uta-Maria Billhardt, Dr. Erich F. Paulus, Dr. Jan W. Bats and Prof. Dr. Hartmut Fuess

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404421

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      Addition of cyclohexylamine to a permethylated dienylketene furnishes rac-1 and rac-2 (X-ray structure analysis). Conventional spectroscopic data do not provide sufficient information to decide whether the 1,2-, 1,4-, or 1,6-adduct is present. However, new NMR techniques facilitate this, as described in the following article.

    12. Determination of Connectivities via Small Proton-Carbon Couplings with a New Two-Dimensional NMR Technique (pages 444–445)

      Prof. Dr. Horst Kessler, Christian Griesinger and Jörg Lautz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404441

      The novel two-dimensional NMR technique H,C-COLOC enabled the constitutions of the photolysis products 1 and 2 referred to in the preceding article to be determined. In H,C-COLOC spectroscopy, use is made of proton-carbon coupling over two and three bonds. This technique, in which the homonuclear proton coupling are absent, offers several advantages over conventional H,C shift correlations using long-range couplings.

    13. Pigments from the Cap Cuticle of the Bay Boletus (Xerocomus badius) (pages 445–447)

      Dr. Bert Steffan and Prof. Dr. Wolfgang Steglich

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404451

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      A natural product with the unusual naphtho[1,8-bc]pyrandione chromophore is badion A 1, the brown pigment of the cap cuticle of the bay boletus. 1 is derived biogenetically from a trihydroxypulvinic acid present in the fungus.

    14. One-Step Entry to N-Cyanimines and to N,N′-Dicyanoquinonediimines, a Novel Class of Electron-Acceptors (pages 447–448)

      Dipl.-Chem. Alexander Aumüller and Dipl.-Chem. Siegfried Hünig

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404471

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      The first N,N′-dicyanoquinonediimines 3 could be synthesized by reaction of quinones 1 with 2 in the presence of TiCl4. Applications of 3 are discussed in the following article.

    15. Crystal Structure and Conductivity of a Novel Charge-Transfer Complex of N,N′-Dicyano-1,4-naphthoquinonediimine and Tetrathiafulvalene (pages 449–450)

      Dipl.-Chem. Alexander Aumüller, Dr. Erich Hädicke, Prof. Dr. Siegfried Hünig, Dipl.-Phys. Albin Schätzle and Dr. Jost Ulrich von Schütz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404491

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      The structural analogy between N,N′-dicyanoquinonediimines, such as 1, and tetracyanoquinodimethanes suggests that it should be possible to prepare CT-complexes from 1 and the “standard donor” 2. The complex formed from 1 and 2 (X-ray structure analysis) is, in fact, characterized by electrical conductivity.

    16. Peptide Structures of the Alamethicin Sequence: The C-Terminal α/310 Helical Nonapeptide and Two Pentapeptides with Opposite 310 Helicity (pages 450–453)

      Dr. Roland Bosch, Prof. Dr. Günther Jung, Dr. Heribert Schmitt, Prof. Dr. George M. Sheldrik and Prof. Dr. Werner Winter

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404501

      A natural oligopeptide with α-aminoisobutyric acid residues (Aib), which reduce the conformation space, is alamethicin. This icosapeptide antibiotic, as an ionophoric, membrane pore former, is a model compound for the excitability of nerve membranes. Interesting helical structures have now been discovered in the synthetic segments of such compounds: thus, 2 forms a right-handed 310 helix; in contrast, 1 forms a left-handed 310 helix! Previously, only one other 3math image helix was known.

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    17. Oxidation with Palladium Salts: Catalytic Preparation of Allyl Acetates from Monoolefins Using a Three-Component Oxidation System (pages 453–454)

      Dr. Andreas Heumann and Prof. Dr. Björn Åkermark

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404531

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      The selective conversion of monoolefins into allyl acetates can be achieved using a novel catalyst system. Reaction 1 [RIGHTWARDS ARROW] 2 (up to 95% yield) exemplifies this. Other cycloalkenes afford 60–90% yield, while open-chain alkenes can give rise to isomers.

    18. Photochemical Generation of Triphenylsilylboranediyl (C6H5)3SiB: from Organosilylboranes (pages 454–455)

      Dr. Bernd Pachaly and Prof. Dr. Robert West

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404541

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      A carbene- or nitrene-analogous boron species, the title compound 1, was generated by photolysis of RB(SiPh3)2 or B(SiPh3)3 and detected by trapping reactions. 1 inserts into C[BOND]H and C[BOND]O bonds and cycloadds to C[TRIPLE BOND]C bonds to yield borirenes such as 2.

    19. 3-Allyl)(η4-butadiene)(η5-cyclopentadienyl)-zirconium, a System of Isomeric Monocyclopentadienylzirconium(II) Compounds (pages 455–456)

      Priv.-Doz. Dr. Gerhard Erker, Klaus Berg, Prof. Dr. Carl Krüger, Dr. Gerhard Müller, Klaus Angermund, Dr. Reinhard Benn and Gerhard Schroth

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404551

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      Ligands which open “upwards” and “downwards” cause the isomerism in the ZrII complexes 1 and 2. Depending on the conditions, successive treatment of Cp2ZrCl2 with allylMgCl and “butadiene-Mg” gives pure 1 or a mixture of 1 and 2. Irradiation of 1 at −40°C converts it almost quantitatively into 2, which isomerizes to 1 on heating.

    20. Ferrocenium Salts—The First Antineoplastic Iron Compounds (pages 456–457)

      Priv.-Doz. Dr. Petra Köpf-Maier, Prof. Dr. Hartmut Köpf and Prof. Dr. Eberhard W. Neuse

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404561

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      The suprising activity of the action of 1 against Ehrlich ascites tumor in mice must be explainable in terms other than that of the activity of the metallocene dihalogenides of d-electron-deficient transition-metals, since the anions in 1 are not coordinated but bound in a salt-like way. Ferrocene is inactive in the same test.

    21. Highly Enantioselective Alkylation of Tetrahydroisoquinolines via a Valine Chiral Auxiliary; Asymmetric Synthesis of (S)-Isoquinoline Alkaloids (pages 458–459)

      Prof. Dr. A. I. Meyers, Dr. Michael Boes and Daniel A. Dickman

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404581

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      The use of naturally occurring amino acids as a source of chirality offers enormous advantages in enantioselective syntheses. With an L-valinol derivative, readily accessible from L-valine, 1 was initially N-alkylated. From the compound 2 thus obtained, enantiomerically pure 3 can be prepared.

    22. First Evidence for an Intermediate Nitrilo-λ5-phosphane (pages 459–460)

      Ghislaine Sicard, Antoine Baceiredo, Dr. Guy Bertrand and Dr. Jean-Pierre Majoral

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404591

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      (iPr2N)2PN—a nitrene or a nitrile analogue? As suggested by ab initio calculations on H2PN, the intermediate compound 2, obtained from azide 1, proves to be a “nitrile” in trapping reactions.

    23. Nickel-Catalyzed Reduction of Carbon Monoxide by Hexamethyldisilane: a New Reaction Leading to a Novel Synthesis of Siloxanes (pages 460–461)

      Prof. Dr. K. Peter C. Vollhardt and Dr. Zhen-Yu Yang

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404601

      CO as oxidizing agent for Me3Si[BOND]SiMe3 facilitates a novel synthesis of siloxanes. The catalyst used is nickel on kieselgur. Particularly good conversions and yield were obtained in the presence of H2. In this way, “C” is converted into CH4 (R[DOUBLE BOND]CH3).

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  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Book Review: The Chemistry of the Allenes. Edited by S. R. Landor (pages 461–462)

      Gerhard Himbert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404611

    2. Book Review: Enrichment Techniques for Inorganic Trace Analysis. By A. Mizuike (page 463)

      Manfred Grasserbauer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404631

    3. Book Review: Electron and Ion Microscopy and Microanalysis. By L. E. Murr (pages 464–466)

      Käthe Müller

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198404641

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