Angewandte Chemie International Edition in English

Cover image for Vol. 24 Issue 12

December 1985

Volume 24, Issue 12

Pages 1009–1092

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 12/1985)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510091

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      The cover shows two toadstools (Agaricus xanthoderma). These fungi stain intense chrome yellow when bruised and develop a phenol-like odor. They turn orange-yellow upon treatment with alkalis. Furthermore, extracts of these toadstools exhibit antibiotic activity. All these remarkable effects are caused by compounds that are surprising to encounter in nature. Further details are reported by W. Steglich et al. on page 1063 (photograph: A. Bresinsky, Regensburg).

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 12/1985)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510092

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Author Index
    6. Subject Index
    1. Molecular Mechanism of Action of the Antibiotic Rifampicin (pages 1009–1014)

      Prof. Dr. Guido R. Hartmann, Dipl.-Biol. Peter Heinrich, Dipl.-Biol. Margit C. Kollenda, Dipl.-Biol. Bernhard Skrobranek, Dr. Maximilian Tropschug and Dipl.-Biol. Wolfgang Weiß

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510093

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      The lipophilic antibiotic rifampicin has long been used successfully to treat tuberculosis. Its mechanism of action, however, has only recently been elucidated. Rifampicin disrupts the metabolism of Eubacteria by binding strongly to a single, highly specific binding site of the DNA-dependent RNA polymerase, thereby inhibiting RNA synthesis.

    2. Error Rates of the Replication and Expression of Genetic Information (pages 1015–1025)

      Dr. Uwe Englisch, Dr. Dieter Gauss, Dr. Wolfgang Freist, Dr. Sabine Englisch, Dr. Hans Sternbach and Prof. Dr. Friedrich von der Haar

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510151

      The transcription and translation of genetic information requires a high level of accuracy. In many cases, the difference in binding energies of the correct and incorrect substrates is insufficient to guarantee such accuracy. Therefore, a proofreading step and, if necessary, a correction step are required. The wrong intermediate thereby undergoes enzymatic hydrolysis.

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    3. The Role of Hydrothermal Synthesis in Preparative Chemistry (pages 1026–1040)

      Prof. Dr. Albrecht Rabenau

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510261

      Quartz single crystals for oscillators, synthetic emeralds, CrO2 for magnetic tapes, silicate-rich zeolites—these and many other substances may be prepared by hydrothermal synthesis. These heterogeneous reactions, which are carried out in aqueous medium above 100°C and 1 bar, represent a special case of chemical transport phenomena. Under hydrothermal conditions, substances that are otherwise only sparingly soluble dissolve readily as complexes, the formation of which may involve water or “mineralizers.”

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Author Index
    6. Subject Index
    1. Novel Reactions of Acyl Halides with Bis(trimethylsilyl) Telluride: C,Te and C,C Bond Formation (pages 1041–1042)

      Dr. Tevfik Severengiz, Prof. Dr. Wolf-Walther du Mont, Priv.-Doz. Dr. Dieter Lenoir and Heike Voss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510411

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      Tellurium compounds are increasingly used in organic synthesis. The first telluroacetic acid derivative, the ester 3, was identified by its mass spectrum. 3 decomposes spontaneously to give (Z)- and (E)-2,3-bis(trimethylsiloxy)-2-butene and tellurium. The starting material 2 is obtainable from 1 and acetyl chloride.

    2. Non-Induced, Highly Diastereoselective Intramolecular Ene Reactions of 1,7-Dienes to trans-1,2-Disubstituted Cyclohexanes (pages 1042–1043)

      Prof. Dr. Lutz F. Tietze and Dipl.-Chem. Uwe Beifuss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510421

      The terminology of stereoselective synthesis is rapidly coming to resemble the legendary Tower of Babel. “Induced” and “non-induced diastereoselective” are the most recent newcomers. Whether these unquestionably useful terms will find acceptance is a matter for the future to decide. They were introduced in order to explain the title reaction in which 1,2-disubstituted cyclohexanes with a trans: cis selectivity of > 99 : 1 are formed.

    3. Bicyclic Acetals from Oxacarbenes (pages 1043–1044)

      Prof. Dr. Michael Pirrung

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510431

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      Two annelated tetrahydrofuran structural units—partial structures of the aflatoxins and caryoptins—can be prepared by irradiation of cyclobutanones such as 1. Thus, the cyclic acetal 2 is formed by an intramolecular trapping reaction of a photochemically generated oxacarbene.

    4. Cyclopropyl-Substituted Aminocyclopropane Carboxylic Acid (Cyclopropyl-ACC)—an Investigation of the Mechanism of Ethylene Biosynthesis (pages 1044–1045)

      Prof. Dr. Michael Pirrung and Dipl.-Chem. Gerard M. McGeehan

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510441

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      The biosynthesis of ethylene, which functions as a fruit-ripening hormone in plants, from methionine via aminocyclopropane carboxylic acid is inhibited by 1. In the presence of apple tissue, 1 slowly forms 1,4-pentadiene 2 via a radical pathway; this is accompanied by inhibition of the ethylene-forming system.

    5. PdII-Catalyzed Stereoselective Bis-Lactonization (pages 1045–1046)

      Dr. Y. Tamaru, H. Higashimura, K. Naka, M. Hojo and Prof. Dr. Z. Yoshida

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510451

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      The formation of bis-lactones of type 2 from 1 (X[DOUBLE BOND]H) and CO is catalyzed by PdII. Substituents on C-2 and C-3 are largely tolerated. In comparison, 1 (X[DOUBLE BOND]Ac) forms only open-chain 1,3-dienes in the presence of Pd0.

    6. Synthesis of Dipleiadiene by “Serendipity” (pages 1046–1048)

      Prof. Dr. Emanuel Vogel, Brigitte Neumann, Dr. Wolfgang Klug, Dr. Hans Schmickler and Dr. Johann Lex

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510461

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      A “Perturbed [16]annulene”—this is one way to view the much discussed dipleiadiene, 1, which has finally been obtained in the course of an investigation having an entirely different goal. Although 1 is formally a naphthalene that is peri-bridged by butadiene structural units, it exhibits pronounced paratropism.

    7. 1,4-Photocycloaddition of α-Morpholinoacrylonitrile to 1-Acylnaphthalenes (pages 1048–1049)

      Prof. Dr. Dietrich Döpp, Prof. Dr. Carl Krüger, Dipl.-Chem. Hamid Reza Memarian and Dr. Yi-Hung Tsay

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510481

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      The captodative olefin 2 can undergo smooth addition to acylnaphthalene 1 (R[DOUBLE BOND]H, Me, Ph) to give the 1,4-photocycloadduct 3. Such reactions of naphthylcarbonyl derivatives are extremely rare and synthetically useful.

    8. Oxidation of 2-Propanol at Ti/Cr2O3 Anodes (pages 1049–1051)

      Dipl.-Chem. Harry Schulz and Prof. Dr. Fritz Beck

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510491

      Quantitative current yields without formation of CrIII salts are achieved in the oxidation of 2-propanol to acetone at ceramic Ti/Cr2O3 anodes. The postulated reaction mechanism is analogous to that formulated by Westheimer for homogeneous oxidation with chromic acid. The lifetimes of the electrodes, however, are too short for use of the reaction on an industrial scale.

    9. Elucidation of the Structure of Epidermin, a Ribosomally Synthesized, Tetracyclic Heterodetic Polypeptide Antibiotic (pages 1051–1053)

      Dr. Hermann Allgaier, Prof. Dr. Günther Jung, Priv.-Doz. Dr. Rolf G. Werner, Dr. Ursula Schneider and Prof. Dr. Hans Zähner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510511

      A decosapeptide that is highly effective against acne has been isolated from a culture filtrate of Staphylococcus epidermidis Tü 3298. The molecule contains four disulfide bridges derived from meso-lanthionine, β-methyllanthionine, and the newly discovered amino acid S-(2-aminovinyl)-D-cysteine. The structure elucidation was achieved by enzymatic and hydrolytic fragmentation and desulfurization with Raney nickel followed by sequence analysis.

    10. Isolation of the Stable Silaketimine tBu2Si[DOUBLE BOND]N[BOND]SitBu3 (pages 1053–1054)

      Prof. Dr. Nils Wiberg, Klaus Schurz and Dr. Gerd Fischer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510531

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      The Si[DOUBLE BOND]N bond of the silaketimine 2, which is obtained by “thermal salt elimination” from the lithium compound 1, can undergo numerous addition reactions. For example, reaction with methyl vinyl ether affords the [2+2] cycloadduct 3.

    11. Synthesis of 6-Substituted Purines and Ribonucleosides with N-(6-Purinyl)pyridinium Salts (pages 1054–1055)

      Doc. Dr. Ryszard W. Adamiak, Dr. Ewa Biała and Dr. Bohdan Skalski

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510541

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      The pyridinium group at C-6 of the purine 1, R[DOUBLE BOND]Me, has proved to be a good leaving group, making possible an efficient two-step synthesis of the biochemically important derivatives 2, X[DOUBLE BOND]N3, SCH2CH2OH, OCH3. Older methods, which required more steps, afforded lower overall yields.

    12. Selectivity of the Anodic Oxidation of CH- and CH2-Groups; Selective Oxidation of Steroids at C-6 (pages 1055–1056)

      Dipl.-Chem. Annegret Hembrock, Prof. Dr. Hans J. Schäfer and Dr. Gesine Zimmermann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510551

      Anodic oxidation results in comparatively good chemoselectivity; the ratio of attack at tertiary to attack at secondary C atoms is 12 : 1 for decalin. The regioselectivity of anodic oxidation may be controlled by inductive effects in the case of chlorides (e.g., chlorocyclohexane) and fatty acids. Remarkably, the steroids androstane and cholestane undergo oxidation mainly at C-6.

    13. Bis(2,4,6-tri-tert-butylphenyl)bicyclotetraphosphane (pages 1056–1057)

      Ralf Riedel, Dr. Hans-Dieter Hausen and Prof. Dr. Ekkehard Fluck

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510561

      Only one bond of the P4 tetrahedron is opened to form the title compound 1, a derivative of P4H2. 1, along with the diphosphene derivative 2, was isolated as orange, air-stable crystals (R[DOUBLE BOND]2,4,6-tri-tert-butylphenyl).

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    14. Computer-Controlled Precipitation of Metal Hydroxides and Hydrous Oxides—Preparation of Manganese Dioxide Having Uniform Particle Sizes (pages 1057–1058)

      Dr. Dieter H. Buss, Dipl.-Chem. Gottfried Schaumberg and Prof. Dr. Oskar Glemser

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510571

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      Manganese dioxide with both very small and very large surface areas and uniform particle sizes was prepared from Mn(NO3)2 and KMnO4 at pH 1 and 2 and at pH 0 (see figure), respectively. A computer controlled the mixing of the reagents so that the potential remained constant. The reagents were used in nearly stoichiometric amounts.

    15. 4-[Tri(n-butyl)phosphonio]-2,5-diselenoxo-1,3-diselenacyclopentanide (pages 1058–1059)

      Prof. Dr. Heinz P. Fritz, Dr. Gerhard Müller, cand. chem. Gabriele Reber and Dipl.-Chem. Michael Weis

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510581

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      A new type of phosphorus ylide is represented by the title compound 1, which is obtained as dark red, flat prisms in high yields from CSe2 and nBu3P. Derivatives of 1 might exhibit the properties of “organic metals.”

    16. o,p′-Dibenzene (pages 1059–1060)

      Dipl.-Chem. Ralf Braun, Dipl.-Chem. Matthias Kummer, Prof. Dr. Hans-Dieter Martin and Prof. Mordecai B. Rubin

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510591

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      A new, theoretically interesting, unstable benzene dimer, the title compound 1, was synthesized by photolysis of the barrelene-o-quinone adduct. The Arrhenius parameters for the decomposition of 1 to form benzene were determined.

    17. [(η5-C5Me5)2Fe2S4] and [(η5-C5Me5)2Co2S4], Two Novel Bis(pentamethylcyclopentadienylmetal) Complexes Rich in Sulfur (pages 1060–1061)

      Prof. Dr. Henri Brunner, Norbert Janietz, Walter Meier, Gertrud Sergeson, Dr. Joachim Wachter, Dipl.-Chem. Thomas Zahn and Prof. Dr. Manfred L. Ziegler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510601

      Thumbnail image of graphical abstract

      The wide range of coordination possibilities for disulfur ligands is exemplified by the title compound. The Fe2 complex contains two Smath image ligands that are arranged perpendicularly to each other, while the Co2 complex shown on the right represents a new type of structure.

    18. Multiple Bonds between “Naked” Lead and Transition Metals—The First Example (pages 1062–1063)

      Prof. Dr. Wolfgang A. Herrmann, Heinz-Josef Kneuper and Dr. Eberhardt Herdtweck

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510621

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      A substituent-free Pb atom that is bonded though double bonds to two organomanganese fragments is present in complex 2, which is surprisingly easy to prepare from the mononuclear complex 1 and PbCl2 in tetrahydrofuran (THF). The MnPbMn skeleton is nearly linear.

    19. The Chemistry and Antibiotic Activity of the Toadstool Agaricus xanthoderma (Agaricales) (pages 1063–1065)

      Dipl.-Chem. Sabine Hilbig, Thomas Andries, Prof. Dr. Wolfgang Steglich and Prof. Dr. Timm Anke

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510631

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      The toadstool Agaricus xanthoderma, which has a phenol-like odor, exhibits interesting properties. The strong antibiotic activity of its extract is due to 4-diazo-2,5-cyclohexadien-1-one 1; the yellow coloration of bruised fungi is caused by the diazamerocyanin 2 and by a p-hydroxyphenylazo derivative of glutamic acid.

    20. Simply Substituted Boraethenes (pages 1065–1066)

      Prof. Dr. Günther Maier, Dipl.-Chem. Jochem Henkelmann and Dr. Hans Peter Reisenauer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510651

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      The limits of stability of boraethenes—not containing bulky substituents—appear to have been reached with 2. Compounds 2 are formed by the thermal cycloreversion of Diels–Alder adducts and can be isolated in an argon matrix or trapped with, e.g., benzophenone (X[DOUBLE BOND]OCH3, N(CH3)2).

    21. Asymmetric Synthesis of (R)-β-(Alkoxycarbonyl)aspartic Diesters (Derivatives of (R)-Asa) with a Chiral Cationic Amino Acid Synthon (pages 1066–1067)

      Prof. Dr. Ulrich Schöllkopf, Dr. Hans-Jürgen Neubauer and Dipl.-Chem. Manfred Hauptreif

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510661

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      The scope of application of the bislactim ether method in the synthesis of amino acids has been broadened by the use of the chloride 1. Compound 1 serves as a cationic synthon, which reacts with nucleophiles. A prime example is the synthesis of 2, which can be hydrolyzed to give the title compounds 3.

    22. Asymmetric Addition of a Chiral Cyclic Phosphite to a Cyclic Imine—Synthesis of Phosphonic Acid Analogues of D- and L-Penicillamine (pages 1067–1068)

      Dr. Inga Hoppe, Prof. Dr. Ulrich Schöllkopf, Martin Nieger and Dr. Ernst Egert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510671

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      α-Amino phosphonic acids, analogues of α-amino carboxylic acids, are of interest because of their potential biological activity. The title reaction makes possible the preparation of (easily separated) diastereomers, which can be saponified to give penicillamine analogues (R[DOUBLE BOND]C(CH3)2OCH3).

    23. Acylsilanes via Oxidation of Phosphonium Ylides: The First Synthesis of Bis(trimethylsilyl)ketone and Its Use as a CO2⊖ Equivalent (pages 1068–1069)

      Prof. Dr. Alfredo Ricci, Dr. Mariella Fiorenza, Dr. Alessandro Degl'Innocenti, Dr. Giancarlo Seconi, Dr. Pasquale Dembech, Dipl.-Chem. Konard Witzgall and Prof. Dr. Hans Jürgen Bestmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510681

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      A highly selective nucleophilic formylation is possible under mild conditions with bis(trimethylsilyl) ketone 1, a strawberry-colored oil. Thus, it reacts for example, with 2-cyclohexenone, undergoing 1,4-addition to give 2, which in turn yields 3 in the presence of moisture.

    24. Bis(tert-butyl)diphosphene as Building Block of a Trichromium Cluster. A Novel Type of Coordination of Diphosphenes (pages 1069–1070)

      Dipl.-Chem. Jutta Borm, Prof. Dr. Gottfried Huttner and Dr. Laszlo Zsolnai

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510691

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      A Z-diphosphene fragment as side-on and end-on coordinated ligand as well as a μ3-P--tBu bridge are present in the triangulo Cr3 cluster 1, which is formed by thermal decomposition (100°C) of tBuP[Cr(CO)5]2.

    25. Synthesis of the First α-Methylene-β-peroxylactone—Regiospecific Ene Reaction of 1O2 with α,β-Unsaturated Carboxylic Acids (pages 1070–1071)

      Prof. Dr. Waldemar Adam and Dr. Axel Griesbeck

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510701

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      5-Methyl-4-methylene-1,2-dioxolane-3-one 2 exhibits unexpectedly high thermal stability. The first α-methylene-β-peroxylactone was obtained by regiospecific photooxygenation of the α,β-unsaturated carboxylic acid 1 to give the hydroperoxide followed by acid-catalyzed dehydration.

    26. Sensitized UV/Laser Photolysis of Azoalkanes: Conformational Influences on Intersystem-Crossing and Lifetimes of Triplet Diradicals (pages 1071–1072)

      Prof. Dr. Waldemar Adam, Dr. Klaus Hannemann and Prof. Dr. R. Marshall Wilson

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510711

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      Confirmation of the theory of Salem and Rowland that the position of radical orbitals determines the lifetimes of triplet diradicals has been achieved by trapping of the diradicals 1a–1c as the peroxides. The lifetime decreases by more than four orders of magnitude on going from 1a to 1c.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Author Index
    6. Subject Index
    1. Book Review: Chemistry and Technology of Water-Soluble Polymers. Edited by C. A. Finch (page 1073)

      Hans-Helmut Görtz and Jürgen Hartmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510731

    2. Book Review: Solid State Chemistry and its Applications. By A. R. West (page 1073)

      Martin Jansen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510732

    3. Book Review: Amorphe und glasartige Festkörper. By A. Feltz (pages 1073–1074)

      Hans Georg von Schnering

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510733

    4. Book Review: Allenes in Organic Synthesis. By H. E. Schuster and G. M. Coppola (page 1074)

      Henning Hopf

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510741

  4. Author Index

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Author Index
    6. Subject Index
    1. Author Index, 1985 (pages 1075–1079)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510751

  5. Subject Index

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Author Index
    6. Subject Index
    1. Subject Index, 1985 (pages 1080–1092)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198510801

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