Angewandte Chemie International Edition in English

Cover image for Vol. 19 Issue 10

October 1980

Volume 19, Issue 10

Pages 749–840

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 10/1980)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198007491

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 10/1980)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198007492

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Pharmaceutical Chemistry Today—Changes, Problems, and Opportunities (pages 749–761)

      Prof. Dr. Horst König

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198007493

      The search for new pathways in pharmaceutical research means that the medicinal chemist's professional activities are currently in a state of change: concepts from molecular biology are increasingly influencing synthetic strategy. The modern repertory of preparative chemistry is supplemented by enzymatic, biotechnological, and genetic engineering methods for the synthesis of new classes of active compounds. Structure-activity relationships are used to rationalize the search for promising derivatives. Examples of recent “lead substances” derived from nature are small peptides, e.g. enkephalins and oxytocin, as well as prostaglandins and thromboxanes.

    2. The Synthesis of Unusual Organic Molecules from Azoalkanes. New analytical methods (33) (pages 762–779)

      Prof. Dr. Waldemar Adam and Dr. Ottorino De Lucchi

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198007621

      Thumbnail image of graphical abstract

      Strained, sterically hindered, fluxional, antiaromatic, etc., molecules, including polycyclics and cage compounds, have been synthesized by elimination of nitrogen from azoalkanes. Some appropriate examples are shown below.

    3. Mechanistic Aspects of Diels-Alder Reactions: A Critical Survey (pages 779–807)

      Prof. Dr. Jürgen Sauer and Prof. Dr. Reiner Sustmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198007791

      Thumbnail image of graphical abstract

      Attempts to elucidate the mechanism of the fifty-year old classical [4 + 2]-cycloaddition reaction have been undertaken with a formidable armamentarium of methods. Paying due attention to all experimental and theoretical criteria, an attempt is made to distinguish between the mechanistic alternatives of a one-step reaction versus a two-step reaction.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Diagonal Interaction in the Four-Membered Ring. Experimental Demonstration of a Dominating Circumannular Conjugation: 5,6-Dimethylenebicyclo[2.1.1]hexane (pages 807–809)

      Prof. Dr. Hans-Dieter Martin, Mirjana Eckert-Maksić and Dipl.-Chem. Bernhard Mayer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008071

      Thumbnail image of graphical abstract

      Which interaction predominates in planar 1,3-dimethylenecyclobutane (1): circumannular through-bond conjugation or transannular through-space conjugation? PE spectroscopic comparison with compounds (2)-(4) suggests the former alternative.

    2. Olefin-Insertion into Cobalt(d8) Complexes—Structure of Ethylene(phenyl)tris(trimethylphosphane)cobalt (pages 809–810)

      Prof. Dr. Hans-Friedrich Klein, Dr. Reinhard Hammer, Dipl.-Chem. Joachim Gross and Dr. Ulrich Schubert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008091

      Thumbnail image of graphical abstract

      Reversible insertion of ethylene has been observed with the new hydridocobalt complex (1). The likewise new complexes (2) and (3) are unable to undergo this reaction, in spite of their apparently favorable geometry. (1) ⇌ (PMe3)3Co[BOND]CH2[BOND]CH3

    3. The Nitrile Function of Tetracyanoethylene as Dienophile in Diels-Alder Reactions (pages 810–811)

      Prof. Dr. Klaus Burger and Dr. Herbert Goth

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008101

      Thumbnail image of graphical abstract

      Surprising Diels-Alder reactions take place with the standard dienophile tetracyanoethylene and the heterodienes (1). Instead of the C[DOUBLE BOND]C group, the C[TRIPLE BOND]N groups functions as dienophile: this has not been observed previously in Diels-Alder reactions.

    4. 13C-NMR Study of Protonated Thioketones in Superacidic Media: Significance of Mercaptocarbenium Ion Contributions (pages 811–812)

      Prof. Dr. George A. Olah, Dr. Tadashi Nakajima and Dr. G. K. Surya Prakash

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008111

      Thumbnail image of graphical abstract

      The products of protonation of thioketones, ketones, and two selenoketones by superacids have been compared by 13C-NMR spectroscopy. The effects detected can only be explained in terms of significant participation of the mercaptocarbenium form (A). The analogous form is known to play no role in the case of ketones.

    5. Thiobenzoyl Cations (pages 812–813)

      Prof. Dr. George A. Olah, Dr. G. K. Surya Prakash and Dr. Tadashi Nakajima

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008121

      Thumbnail image of graphical abstract

      Thiobenzoyl cations have been characterized for the first time by 13C-NMR studies in superacids. The contribution of the thioketene-like forms is significant, whereas that of Ph[BOND]C[TRIPLE BOND]S can be neglected.

    6. Donor-Acceptor Substituted Cyclopropanes: Synthesis and Ring Opening to 1,4-Dicarbonyl Compounds (pages 813–814)

      Dr. Hans-Ulrich Reissig and Elisabeth Hirsch

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008131

      Thumbnail image of graphical abstract

      Readily accessible starting compounds for 4-oxoesters (2) and 3-formyl esters (2), R1 = H, have been found in the silyloxy-substituted cyclopropanecarboxylic esters (1). Their ring opening takes place smoothly under practically neutral conditions.

    7. Competing [3+4]- and [2+4]-Cycloadditions of Allenyl Cations (pages 814–816)

      Dr. Herbert Mayr and Inge K. Halberstadt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008141

      Thumbnail image of graphical abstract

      A facile synthesis of bicyclo[3.2.1]octa-2,6-dienes (3), R1 = alkyl, and 5-(aryl-methylene)norbornenes (4), R1 = aryl, is possible by cycloaddition of allenyl cations (2) to cyclopentadiene. (2) was generated from propargyl halides (1) with catalytic amounts of ZnCl2 in ether/CH2Cl2.

    8. Oxopropenylation of Grignard Compounds with 3-Ethoxyacroleins (pages 816–817)

      Dipl.-Chem. Klaus Rustemeier and Prof. Dr. Eberhard Breitmaier

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008161

      Aldehydes of type (3) have been synthesized from bromides R1Br via the Grignard compounds (1) and substituted 3-ethoxyacroleins (2). This communication reports over 20 examples.

      • equation image
    9. Benzophenonedilithium as Complex with Tetrahydrofuran and Tetramethylethylenediamine (pages 817–818)

      Prof. Dr. Borislaw Bogdanović, Priv.-Doz. Dr. Carl Krüger and Dr. Bernd Wermeckes

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008171

      Thumbnail image of graphical abstract

      The complex (1) containing the benzophenone dianion could be isolated and characterized by X-ray structure analysis. (1) forms violet highly air- and moisture-sensitive crystals from THF/TMEDA. The complex is of interest, inter alia, as a model for polymetalated 1,6,6aλ4-trithiapentalene.

    10. Catalytic Synthesis of Magnesium Hydride under Mild Conditions (pages 818–819)

      Prof. Dr. Borislav Bogdanović, Dr. Shih-tsien Liao, Manfred Schwickardi, Dipl.-Chem. Peter Sikorsky and Ing. (grad.) Bernd Spliethoff

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008181

      Magnesium hydride, of potential use for reversible storage of hydrogen, has now been synthesized by a method proceeding under mild conditions and which can be performed on a large scale. Especially active catalysts are obtained by reaction of anthracenemagnesium with halides of chromium, titanium, or iron in THF. These solutions are catalytically active at 20°C and under normal pressure.

    11. New Prostacyclin Analogues (pages 819–820)

      Dr. Wilhelm Bartmann, Dr. Gerhard Beck, Dr. Jochen Knolle and Dr. R. Helmut Rupp

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008191

      Thumbnail image of graphical abstract

      The highly active prostacyclin (1) cannot be used therapeutically owing to its extremely short half-life (only 3 min in water at 37°C pH 7.5). Methyl esters of the three analogues having the partial structure (2), X = O,S, and NH, have now been synthesized from an industrially available starting compound. The analogues exhibit interesting biological properties.

    12. 2-Vinylidene-2H-indene (pages 821–822)

      Dipl.-Chem. Reinhard Schulz, Prof. Dr. Armin Schweig, Prof. Dr. Curt Wentrup and Dipl.-Chem. Hans-Wilhelm Winter

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008211

      Thumbnail image of graphical abstract

      The deep-blue product generated from (1) by flash pyrolysis is regarded as 2-vinylidene-2H-indene (2) on the basis of the IR spectrum (at −196°C) and the temperature-dependent PE spectrum. The measured vertical ionization potentials are in excellent agreement with the values calculated by various methods.

    13. Synthesis of Cyclic Compounds from Triphenyl(phenyliminovinylidene)phosphorane and Carboxylic Acids (pages 822–824)

      Prof. Dr. Hans Jürgen Bestmann, Dipl.-Chem. Gerold Schade and Dr. Günther Schmid

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008221

      Thumbnail image of graphical abstract

      Intramolecular Wittig reactions to give hetero- and carbocycles (3)–(5) take place on treatment of the phosphorus ylide (1) with oxocarboxylic acids (2). Some annelations to (5) are superior to other methods, partly because no double-bond isomers are formed.

    14. First Insertion Reaction of Carbon Monoxide into a Rhenium-Carbon σ-Bond (pages 824–825)

      Prof. Dr. Ekkehard Lindner and Dipl.-Chem. Günter von Au

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008241

      Thumbnail image of graphical abstract

      Activation of the CO ligands in the new six-membered rhenacycle (1), R = Ph, by AlBr3 permitted the first insertion of CO into a Rh[BOND]C σ-bond. The complex (2) takes up CO at 20°C at normal pressure.

    15. Double Cycloaddition Yielding a Tricyclic Diphosphorane (pages 825–826)

      Prof. Dr. Alfred Schmidpeter, Dr. Werner Zeiss, Dr. Dietmar Schomburg and Priv.-Doz. Dr. William S. Sheldrick

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008251

      Thumbnail image of graphical abstract

      The ordered combination of four acyclic molecules is observed in the reaction of (1) with p-nitrobenzaldehyde (2) to give the tricyclic compound (3). The product was characterized by X-ray structure analysis.

    16. Synthesis of Norbornenes from Cyclopentadiene and Allyl Alcohols in an Acidic Two Phase System (pages 827–828)

      Dr. Heidrun Ernst (née Vathke) and Prof. H. M. R. Hoffmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008271

      Thumbnail image of graphical abstract

      A novel stepwise Diels-Alder type mechanism can be postulated for the reaction of the allyl alcohol (1) with cyclopentadiene in TsOH/pentane. An allyl cation (2) without donor-substituent on the central C atom functions as “dienophile”. Substituted cyclopentenols accompany (3).

    17. Formation of Pyrrolnitrin and 3-(2-Amino-3-chlorophenyl)pyrrole from 7-Chlorotryptophan (pages 828–829)

      Dipl.-Chem. Karl-Heinz van Pée, Dr. Olga Salcher and Prof. Dr. Franz Lingens

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008281

      Thumbnail image of graphical abstract

      Little is known about chlorinations in secondary metabolism. In connection with the biosynthesis of the antifungal antibiotic pyrrolnitrin (2), NO2 in place of NH2, the metabolite (2) has now been isolated for the first time. The intermediates (1) and (3) were elucidated on a previous occasion.

    18. UV Irradiation of Nucleic Acids and Their Components in the Presence of Air (pages 829–830)

      Prof. Dr. Egon Fahr, Dr. Peter Fecher, Dr. Georg Roth and Dr. Peter Wüstenfeld

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008291

      Pyrimidine bases can give different products on UV irradiation in the presence and the absence of air; hence the action of UV radiation in vivo cannot be deduced solely from in vitro experiments conducted with exclusion of air. A remarkable observation made on UV irradiation of cytosine, uracil, thymine, and similar bases in aqueous solution in the presence of air is the elimination of CO. Perhaps CO is formed in nature by such reactions.

    19. Fluoride-Induced Fragmentation of Trimethylsilyloxysulfonates to Form cis-Coupled Hexahydrozulenones (pages 830–831)

      Prof. Dr. Lutz-F. Tietze and Dipl.-Chem. Ulrich Reichert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008301

      Thumbnail image of graphical abstract

      The cis-hydroazulenone system (2) valuable for the synthesis of natural products has become more readily accessible through the title reaction. This novel fragmentation can also be performed in the presence of many functional groups.

    20. Thermal [2 + 2]-Cycloadditions of Tetracyanoethylene to Cyclic Thioenol Ethers (pages 831–832)

      Dr. Siegfried Fries and Prof. Dr. Klaus Gollnick

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008311

      Thumbnail image of graphical abstract

      Annelated tetrahydrothiophenes and thiopyrans(4) have become readily accessible by [2 + 2]-cycloaddition of (1) to cyclic thioenol ethers (2). The reaction proceeds via spontaneously formed deep-blue CT complexes which are transformed into zwitterions.

    21. Thermal Cycloadditions of Dimethyl Acetylenedicarboxylate to Cyclic Enol Ethers and Thioenol Ethers (page 832)

      Prof. Dr. Klaus Gollnick and Dr. Siegfried Fries

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008321

      Thumbnail image of graphical abstract

      A new synthesis of substituted thiophenes is based on [2 + 3]-cycloaddition of acetylenedicarboxylic esters to 2,3-dihydrothiophenes. Transient yellow CT complexes lead to sulfonium ylides which in turn decompose to alkene and thiophene derivatives.

    22. Thermal Additions of Dimethyl Acetylenedicarboxylate to Cyclic Thioenol Ether 1-Oxides with Ring Expansion (page 833)

      Prof. Dr. Klaus Gollnick and Dr. Siegfried Fries

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008331

      Thumbnail image of graphical abstract

      Partially hydrogenated thiepin and thiocin S-oxides have been obtained by hour-long reaction of (1) with (2). Such compounds were not—or hardly—known previously.

    23. A Cationic Ethylene(hydrio)iridium(III) Complex (page 834)

      Dipl.-Chem. Bernhard Olgemöller and Prof. Dr. Wolfgang Beck

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008341

      Thumbnail image of graphical abstract

      The simplest model so far available for an intermediate of catalytic hydrogenation and hydroformylation of olefins is the title compound (1) which could be isolated and characterized by 1H-NMR spectroscopy and by reaction with Re(CO)math image.

    24. One-Electron Oxidation of 1,2-Dithiacycloalkanes (pages 834–835)

      Prof. Dr. Hans Bock and Dr. Udo Stein

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008342

      Thumbnail image of graphical abstract

      The energetically favorable stable radical cation(1) is formed in solution by the action of the reagent AlCl3/CH2Cl2 on 1,3-propanedithiol (via 1,2-dithiolane) or on 1,2,3-trithiane. Combination of PE and ESR data as well as INDO-open shell calculations showed the CS

      SC group of (1) to have time-averaged planarity and high spin density at the sulfur centers.

    25. The Significance of Isoselective Temperatures for the Existence of Linear Free-Energy Relationships (pages 835–836)

      Prof. Dr. Bernd Giese and Woo-Bung Lee

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008351

      How does the variation of reaction partners (Yj) in competition systems influence the isoselective temperature? With the aim of answering this question, the authors examined the reactions of CF2, CCl2, and CBr2 (X1) with the pairs (Yj/Yi) of methylated ethylenes and Me2C[DOUBLE BOND]CH2. Astonishingly, the isoselective temperature does not change in such series of reactions if a common free-energy relationship exists.

      • equation image
    26. (Trifluoromethyl)fluorogermanates (pages 836–837)

      Dr. David J. Brauer, Prof. Dr. Hans Bürger and Dr. Reint Eujen

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008361

      Germanates containing fluorine and trifluoromethyl ligands are generally accessible by the pathways shown below. In aqueous solution X (X = Cl, Br, I) in the starting compound can be quantitatively precipitated by Ag. As expected, the ligand geometry is octahedral in the dianions, and trigonal-bipyramidal in the monoanions.

      • equation image
  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Book Review: Semisynthetic Proteins. By R. E. Offord (page 838)

      Helmut Zahn

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198008382

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