Angewandte Chemie International Edition in English

Cover image for Vol. 24 Issue 10

October 1985

Volume 24, Issue 10

Pages 799–892

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 10/1985)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507991

      Thumbnail image of graphical abstract

      The cover shows a schematic drawing of an antibody used by Niels K. Jerne as an illustration in his Nobel Lecture. In his article the Nobel laureate points out striking analogies between linguistics and immunology. He compares the repertoire of sentences in a language with the antibody repertoire and the components of a generative grammar with the characteristic features of protein structure. Further details are found on page 810ff.

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 10/1985)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507992

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Solid Phase Synthesis (Nobel Lecture) (pages 799–810)

      Prof. Robert Bruce Merrifield

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198507993

      A solid phase as “protecting group” in peptide synthesis—this was the original idea of Bruce Merrifield, who received the 1984 Nobel Prize for Chemistry. In his lecture, he describes the development of the Merrifield synthesis. In principle, all difunctional educts that may be selectively protected at one end and activated at the other can undergo reactions on solid supports.

    2. The Generative Grammar of the Immune System (Nobel Lecture) (pages 810–816)

      Prof. Dr. Niels K. Jerne

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508101

      The basic concepts of immunology and their development as part of biology during the last 100 years is the starting point of Niels K. Jerne's lecture, which he presented on the occasion of accepting the 1984 Nobel Prize for Physiology and Medicine. Each half of an antibody molecule consists of a light polypeptide chain containing about 214 amino acid residues and a heavy polypeptide chain containing a little more than 400 amino acid residues.

    3. From the Structure of Antibodies to the Diversification of the Immune Responce (Noble Lecture) (pages 816–826)

      Dr. Cesar Milstein

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508161

      The unimaginable variety of antibody structures is evidenced by the fact that an animal produces specific antibodies against bacteria, viruses, and other foreign substances, even against substances with which it has had no prior contact. How is this possible? In his lecture, on the occasion of accepting the 1984 Nobel Prize for Physiology and Medicine, Cesar Milstein describes work directed toward answering this question. These investigations have led to, among other things, the development of the hybridoma technique in collaboration with G. Köhler.

    4. Derivation and Diversification of Monoclonal Antibodies (Nobel Lecture) (pages 827–833)

      Prof. Dr. Georges Köhler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508271

      The trick to preparing monoclonal antibodies on a large scale consists in fusing mouse myeloma (tumor) cells with mouse spleen cells that have previously been exposed to an antigen. The hybridoma cells having the desired characteristics are immortal and secrete antibodies with a single specificity. Georges Köhler, who received the 1984 Nobel Prize for Physiology and Medicine, developed this hybridoma technique together with C. Milstein. The number of applications is legion.

    5. Dinuclear Complexes with Predictable Magnetic Properties (pages 834–850)

      Prof. Dr. Olivier Kahn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508341

      The modification of the magnetic properties of a complexed transition-metalion upon formation of binuclear complexes and the magnetic behavior of binuclear complexes containing two different metals is a fascinating area of investigation. The type and strength of the interaction between the metal centers can be influenced by the choice of metal and ligand. In this way, the directed synthesis of a purely, ferromagnetic Cu2+−VO2+ complex was achieved.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Synthesis of 1,2,3-Butatrienecarboxylic Acids (pages 851–852)

      Prof. Dr. Franz W. Nader and Dipl.-Chem. Claus-Dieter Wacker

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508511

      Thumbnail image of graphical abstract

      The first butatrienecarboxylic acids, the triphenyl derivative 1 and the two E/Z isomeric dicarboxylic acids 2 and 3, have been prepared. Whereas 2, R1 = tBu, is configurationally stable in solution at room temperature, 3, R1 = Ph, isomerizes under these conditions; the E form predominates in the equilibrium (R = H).

    2. On the Thermal Behavior of Butatrienecarboxylic Acid Derivatives: Crystal and Molecular Structure of a [4]Radialene Tetracarboxylic Ester (pages 852–853)

      Prof. Dr. Franz W. Nader, Dipl.-Chem. Claus-Dieter Wacker, Prof. Dr. Hermann Irngartinger, Ursula Huber-Patz, Dipl.-Chem. Rainer Jahn and Hans Rodewald

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508521

      Thumbnail image of graphical abstract

      A thermal solid-state reaction with exclusive formation of the all -Z-[4]radialene 1 was observed for dimethyl (E)-1,4-diphenyl-1,2,3-butatriene-1,4-dicarboxylate. The four-membered ring in 1 is very strongly puckered; the substituents form an irregular propeller structure in which the ester and phenyl groups are twisted counter to each other.

    3. Misinterpretation of CC Bonding through Unusually Large 2JCC Values—a Caveat for the Use of INADEQUATE-13C-NMR Spectroscopy (pages 854–855)

      Dr. Hans Bauer, Priv.-Doz. Dr. Joachim Buddrus, Dr. Wolfgang Auf der Heide and Dr. Wolfgang Kimpenhaus

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508541

      Thumbnail image of graphical abstract

      The determination of the constitution of organic compounds via 13C-13C couplings is a relatively new and useful method. Not every coupling constant greater than ca. 25 Hz, howerver, indicates the presence of a CC bond, as found in the case of chlorinated ketones, in particular, cyclobutenone derivatives such as 1. For 1, 2JC-2, C-4 is 64.1 Hz!

    4. Diethyl Thioxomalonate S-Oxide; a Sulfine as Reactive Intermediate (pages 855–856)

      Prof. Dr. Rolf W. Saalfrank and Dipl.-Chem. Walter Rost

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508551

      Thumbnail image of graphical abstract

      The heteroallene 1, formed as an intermediate in the reaction of tetraethoxyallene with thionyl chloride, can be trapped by dimethylbutadien0e in a Diels-Alder reaction before it dimerizes to a 1,2-dithietane.

    5. Do Cp(CO)2Mn Fragments Stabilize Radicals? (pages 856–858)

      Dipl.-Chem. Renate Gross and Priv.-Doz. Dr. Wolfgang Kaim

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508561

      Two classes of paramagnetic manganese complexes can be differentiated by ESR spectroscopy: radical complexes 1, in which radical-anion ligands L⊙⊖ are stabilized by Cp(CO)2Mn1 fragments, and low-spin Mn11 compounds 2, with strongly nucleophilic ligands L.

      • equation image
    6. Reactions in the Ligand Sphere of Iron(II): Synthesis of Crown Ethers (pages 858–859)

      Dr. Kurt Meier and Grety Rihs

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508581

      Thumbnail image of graphical abstract

      The iron sandwich complex 2 containing two [12]crown-4 ligands is formed upon irradiation of the arene-iron complexes 1 in the presence of ethyleneoxide. The Lewis acid activity of the intermediate iron complex that is photochemically formed is decisive for this specific crown ether synthesis. The structure of 2 was determined by X-ray diffraction.

    7. Lithium-Coordinated α-Sulfonyl Carbanions: Synthesis and X-Ray Structure Determination of [{CH2(SO2C6H5)}Li(tmeda)]2 (pages 859–860)

      Priv.-Doz. Dr. Hans-Joachim Gais, Prof. Dr. Hans Jörg Lindner and Dipl.-Ing. Jürgen Vollhardt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508591

      Thumbnail image of graphical abstract

      In order to finally resolve the controversy over the structure of α-lithiated sulfones and α-sulfonyl carbanions, Me[BOND]SO2[BOND]Ph was lithiated in TMEDA and the product, the title compound, was studied by X-ray analysis. It is a dimer in which the Li, S, and O atoms form a flat eight-membered ring. The nearly planar CH2[BOND]S group lies outside the coordination sphere of Li.

    8. Novel C[BOND]O Bond Formation via [3+2] Cycloaddition of Diphenylketene to a Dioxo Metal Moiety (pages 860–861)

      Prof. Dr. Wolfgang A. Herrmann, Ulrich Küsthardt, Prof. Dr. Manfred L. Ziegler and Thomas Zahn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508601

      Thumbnail image of graphical abstract

      The ReO3 group is retained during the [3+2] cycloaddition of diphenylketene to the trioxorhenium(VII) compound 1; the metallacycle 2 precipitates in the form of violet crystals. The reaction could be of use for the oxidation of CC multiple bond systems (R = C6H5).

    9. Skeletal Isomerization of the [Pt3(μ-PPh2)3Ph(PPh3)2] Cluster by Recrystallization in Various Solvents (pages 861–862)

      Dr. Robert Bender, Dr. Pierre Braunstein, Prof. Antonio Tiripicchio and Prof. Marisa Tiripicchio Camellini

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508611

      The solvent used for crystallization determines which of the two structural isomers of [Pt3(μ-PPh2)3Ph(PPh3)2] 1 is formed. The isomer 1a is obtained in crystalline form from toulene/pentane, the isomer 1b · 2CH2Cl2 from CH2Cl2/pentane. The two isomers differ in their Pt[BOND]Pt distances and Pt[BOND]PPh2[BOND]Pt angles.

      • equation image
    10. Polymorphism of an Organolithium Compound: Dilithium 1,2-diphenylbenzocyclobutadienediide · 2 Tetramethylethylenediamine (pages 863–864)

      Prof. Dr. Gernot Boche, Dr. Heinz Etzrodt, Priv.-Doz. Dr. Werner Massa and Gerhard Baum

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508631

      Thumbnail image of graphical abstract

      Two modifications, in which Li atoms occupy different positions, exist for the title compound 1. The polymorphism of this species supports the idea that the structure of organolithium compounds can be modified by packing effects in the crystal.

    11. Electrochemical Methoxylation of Antipyrine (pages 864–865)

      Prof. Dr. Gerd Kaupp, Fatih Köleli and Eleonore Gründken

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508641

      Thumbnail image of graphical abstract

      Regioselective attack on the N-methyl group takes place upon electrolysis of antipyrine in an undivided cell. The product 1 is of interest as, among other things, a model compound for the metabolism of antipyrine, which results in demethylation.

    12. [(η5-C5Me5)(CO)2M[BOND]P[DOUBLE BOND]P(2,4,6-tBu3C6H2)] (M = Fe, Ru), the First Diphosphenyl Complexes (pages 865–866)

      Priv.-Doz. Dr. Lothar Weber and Dipl.-Chem. Klaus Reizig

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508651

      The transition-metal-substituted diphosphenes 2 (M = Fe, Ru) were obtained from the disilylphosphido complexes 1 and a dichlorophosphane. Complexes with M[BOND]P[DOUBLE BOND]P[BOND] structural moieties were previously unknown.

      • equation image
    13. A Photochemically “Switched-on” Crown Ether Containing an Intraannular 4-Methoxyphenylazo Substituent (pages 866–867)

      Prof. Dr. Seiji Shinkai, Kiminori Miyazaki and Prof. Dr. Osamu Manabe

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508661

      The binding of metal ions can be hindered by the intraannular 4-methoxyphenylazo substituent in dibenzo[18]crown-6 analogues in which a [BOND]CH2[BOND]O[BOND]CH2 group is replaced by a (substituted) m-phenylene ring. When the substituent is photochemically flipped out of the cavity, metal ions may be complexed in the manner characteristic of crown ethers.

    14. The First Chemical Partial Synthesis of the Nickel Complex of a Cobyrinic Acid Derivative (pages 867–869)

      Dipl.-Chem. Gerhard Holze and Prof. Dr. Hans Herloff Inhoffen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508671

      Thumbnail image of graphical abstract

      The transmetalation of a vitamin B12 building block was achieved as follows: oxidation of 1, N[DOUBLE BOND]Co(CN)2, to the seco compound, demetalation, reaction with Ni(ClO4)2, and recyclization at 100°C to give 1, M[DOUBLE BOND]NiClO4. Corrinoids of this kind, containing metal ions other than cobalt, were previously only accessible from natural metal-free corrinods or by total synthesis.

    15. Cl2C[BOND]Cl[BOND]Cl⊙⊕, Cl2C[BOND]Cl[BOND]Br⊙⊕, and Br2C[BOND]Br[BOND]Cl⊙⊕ by Gas-Phase Decarbonylation of CX3COY⊙⊕ (pages 869–870)

      Thomas Drewello, Dr. Thomas Weiske and Prof. Dr. Helmut Schwarz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508691

      The long-sought radical cation of carbon tetrachloride has been generated by decarbonylation of Cl3CCOCl⊙⊕ in the gas phase and characterized as the stable isomer Cl2C[BOND]Cl[BOND]Cl⊙⊕. The theoretically predicted properties were experimentally confirmed. The dication CClmath image is known.

    16. Reactions of Per(chloro, fluoro)ethanes with Aryloxide and Alkoxide Ions — Evidence for Chlorophilic Attack on C[BOND]Cl Bonds (pages 871–872)

      Prof. Xing-ya Li, He-qi Pan, Prof. Xi-kui Jiang and Zheng-yun Zhan

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508711

      The synthesis of aryl- and alkyl per(chloro, fluoro) ethyl ethers 2 is achieved by reaction of nucleophiles ROK with the substrates 1 (X, Y[DOUBLE BOND]Cl, F). This is the first confirmed example for the attack of oxygen nucleophiles on the C[BOND]Cl bond. The ethers 2 are only obtainable with difficulty by others routes.

      • equation image
    17. Increased Production of Specific Antibodies by Presentation of the Antigen Determinants with Covalently Coupled Lipopetide Mitogens (pages 872–873)

      Prof. Dr. Günther Jung, Dipl.-Biochem. Karl-Heinz Wiesmüller, Dr. Gerhard Becker, Dr. Hans-Jörg Bühring and Prof. Dr. Wolfgang G. Bessler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508721

      A new concept for the production of antibodies consists in preparing a conjugate from the “lipid membrane anchor” N-palmitoyl-S[2,3-bis(palmitoyl-oxy) propyl]cysteiny1 serine and the antigen—for example, a tetradecapeptide. These conjugates are potent immunogens, which, within a few days, induce the production of high titers of antigen-specific antibodies (IgG and IgM), both in vivo and in vitro, with only one application and without either carrier proteins or Freund's adjuvant. It has already been possible to produce monoclonal antibodies with these new low-molecular-weight, chemically defined conjugates, which are obtainable via Merrifield synthesis.

    18. Enantio- and anti-Diastereoselective Aldol Additions of Acetates and Propionates via O-Silyl Ketene Acetals (pages 874–875)

      Prof. Dr. Günter Helmchen, Dipl.-Chem. Ulrich Leikauf and Dipl.-Chem. Irmtraud Taufer-Knöpfel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508741

      Thumbnail image of graphical abstract

      A direct route to β-hydroxyketones 1a and 1b, which are of importance for naturl product syntheses, starts from the acetates or propionates of the alcohols 2a and 2b. The highly stereoselective aldol condensation is achieved by a Mukaiyama reaction.

    19. A Previously Unrecognized 1H-Azepine Synthesis (pages 875–876)

      Prof. Dr. Hartwig Perst, Priv.-Doz. Dr. Werner Massa, Dipl.-Chem. Michael Lumm and Gerhard Baum

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508751

      The 1H-azepine derivative 1 rather than the cyclohexadienylidenamide 3 was the species obtained by Adams and Brower in 1956, as now revealed by an X-ray analysis. Assignment of the structure on the basis of spectroscopic data was—and still is—not possible in this case. This finding opens up a simple route for the synthesis of other 2-cyano-1H-azepines.

    20. Photochemical Synthesis of an L-Erythrose Building Block and Its use in the Preparation of Methyl 2,3,O-Isopropylidene-β-L-apio-L-furanoside (pages 877–878)

      Dipl.-Chem. Alfred Nehrings, Prof. Dr. Hans-Dieter Scharf and Dr. Jan Runsink

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508771

      Thumbnail image of graphical abstract

      The synthesis of branched carbohydrates, e.g., the title compound 2, from nonsugar building blocks is achieved by a chirally controlled photoaldol reaction. [2+2] Cycloaddition of (−)-8-phenylmenthyl phenylglyoxylate Ph[BOND]CO[BOND]CO2R* to 2,2-dimethyl-1,3-dioxole leads in exo fashion diastereoselectively to 1, one of four possible oxetanes; 1 is then converted in several steps into 2.

    21. Catalytic Hydroboration with Rhodium Complexes (pages 878–879)

      Detlef Männig and Prof. Dr. Heinrich Nöth

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508781

      Thumbnail image of graphical abstract

      The activation of CC double bonds for hydroboration may be achieved using rhodium complexes: e.g., the dioxaborole 1 undergoes preferential addition to the double bond when [CIRh(PPh3)3] is added to the reaction mixture.

    22. Polymeric Tris[trimethyltin(IV)]hexacyanocobaltate(III), a Compound Non-Analogous to “Super Prussian Blue,” and Its Tris[tricyclopentadienyluranium(IV)] Homologue (pages 879–881)

      Dr. Kenan Yünlü, Dipl.-Chem. Nils Höck and Prof. Dr. R. Dieter Fischer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508791

      The coordination polymer 1 with a three-dimensional network of Co atoms is formed as shown below. Distorted octahedral Co(CN)6 structural units are present in 1, which are linked through SnMe3 bridges such that the partial structures …[BOND]Co[BOND]C[TRIPLE BOND]N [RIGHTWARDS ARROW] SnMe3 [LEFTWARDS ARROW] N[TRIPLE BOND]C[BOND]Co[BOND]… are formed. The Sn atoms are coordinated trigonal-bipyramidally. Since, surprisingly, two-thirds of the chains are nonlinear, no super Prussian blue analogue can form; such an analogue should contain cubic Co8 cages.

      • equation image
    23. Regiospecific α-Alkylation of α-Haloalkylidenamines (“α-Haloketimines”) (pages 881–882)

      Dr. Norbert De Kimpe, Dipl.-Ing. Paul Sulmon and Prof. Dr. Niceas Schamp

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508811

      Thumbnail image of graphical abstract

      By masking α-haloketones 1 as α-haloalkylidenamines 2, the α-alkylation of haloketones becomes possible even when hydrogen atoms are present in the α′ position. The anions 3, obtained by the use of lithium diisopropylamide, react with alkyl halides at room temperature to form exclusively C-alkylated products 4.

    24. Photoreactions of N-(1-Pyridinio)amidates in Monolayers and Liposomes (pages 882–883)

      Dipl.-Chem. Michael Haubs and Prof. Dr. Helmut Ringsdorf

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508821

      Thumbnail image of graphical abstract

      Photosensitive monolayers and liposomes can be prepared from amphiphilic pyridinioamidates such as 1 (the “double chain” symbolizes the N(CH2CH2OCOC15H31)2 residue). Their surface properties and stability can be significantly modified by UV radiation. For example, stable liposomes formed from 1 are thereby converted into metastable liposomes consisting of 1,2-diazepines 2.

    25. Construction of Disaccharide N-Glycopeptides—Synthesis of the Linkage Region of the Transmembrance-Neuraminidase of an Influenza Virus (pages 883–885)

      Prof. Dr. Horst Kunz and Dr. Herbert Waldmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508831

      Thumbnail image of graphical abstract

      The glycopeptide fragments 1 and 2 from immunologically interesting N-glyco-proteins can be obtained in a highly selective manner from a cleavable allylester. 1 and 2 are model compounds for the study of recognition mechanisms at cell membrances.

    26. The First [2.1] Phane: a New Helical Molecular Skeleton (pages 885–886)

      Dipl.-Chem. Karl-Heinz Duchêne and Prof. Dr. Fritz Vögtle

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508851

      Thumbnail image of graphical abstract

      The [2.1]phane 1 is rigidly twisted and therefore helical; it is the [m.n]phane with the shortest bridges so far. Its synthesis was carried out in six steps. 1 could be separated into its enantiomers, which are stable up to 200°C.

    27. Primary Adduct, γ-Ketoketene, and Some Subsequent Products of the Reaction of Methyl 6-Oxo-5-phenyl-1,3,4-oxadiazinecarboxylate with Norbornene (pages 886–887)

      Prof. Dr. Manfred Christl, Dr. Ulrike Lanzendörfer, Dipl.-Chem. Maria M. Grötsch and Dipl.-Chem. Joachim Hegmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198508861

      Thumbnail image of graphical abstract

      Two groups that can be easily eliminated by cycloreversion, N2 and CO2, are present in 1, the primary adduct of the title reaction. 1 could be isolated in crystalline form. Elimination of nitrogen affords a γ-ketoketene, the subsequent reactions of which indicate that it exists in equilibrium with a dihydropyrylium-2-olate.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews