Angewandte Chemie International Edition in English

Cover image for Vol. 18 Issue 12

December 1979

Volume 18, Issue 12

Pages 887–981

Currently known as: Angewandte Chemie International Edition

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Author Index
    6. Subject Index
    1. Nodal Nomenclature–General Principles (pages 887–899)

      Prof. Noël Lozac'h, Dr. Alan L. Goodson and Dr. Warren H. Powell

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197908873

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      Fundamental advances in chemical nomenclature can only be expected from new concepts. Nodal nomenclature based on graphs is applicable to all kinds of compounds, leads to unequivocal names, and also permits unequivocal numbering of each node in complicated assemblies of chains and rings.

    2. Developments in Arylnitrene Chemistry: Syntheses and Mechanisms [New synthetic methods (31)] (pages 900–917)

      Dr. B. Iddon, Dr. O. Meth-Cohn, Dr. E. F. V. Scriven, Prof. Dr. H. Suschitzky and Dr. P. T. Gallagher

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909001

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      Ring closure and ring expansion—Characteristic reactions of aryl-and heteroarylnitrenes—provide a convenient entry to nitrogen-containing polycyclic compounds and to azepines and anneiated azepines.

    3. Capto-dative Substituent Effects in Syntheses with Radicals and Radicophiles [New synthetic methods (32)] (pages 917–932)

      Prof. Heinz Günter Viehe, Dipl.-Ing. Robert Merényi, Dr. Lucien Stella and Dr. Zdenek Janousek

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909171

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      Molecules containing an electron acceptor and an electron donor group are substituted in capto-dative (cd) manner cd substituents on the same carbon atom stabilize radicals; the stability of Wurster's salts, known for 100 years, is partly due to this effect. Geminally cd substituted olefins are radicophilic.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Author Index
    6. Subject Index
    1. α-Aminoaldehydes from Enamines and Chloramine-T (page 933)

      Prof. Dr. Ingolf Dyong and Dipl.-Chem. Quan Lam-Chi

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909331

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      A facile entry to the α-amino aldehyde group, which occurs in antibiotic sugars and other natural products, is provided by the reaction of enamines (1) with chloramine T. The conditions are very mild and the yields are high.

    2. Structure of the Dicyanophosphide Ion in a Crown-Ether Sodium Salt (pages 934–935)

      Priv.-Doz. Dr. William S. Sheldrick, Dr. Jürgen Kroner, Dipl.-Chem. Franz Zwaschka and Prof. Dr. Alfred Schmidpeter

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909341

      Comparably large positively and negatively charged structural units are present in the lattice of the 1:1:1: complex of NaP(CN)2, [18]crown-6, and tetrahydrofuran: Na+/crown ether/2 THF and Na+/crown ether/2P(CN)math image. The P(CN)math image ion is planar and bent; the calculated structure is essentially confirmed by X-ray structure analysis. P/CN interaction is slight.

    3. Five-coordinate Tervalent Phosphorus in the Tricyanobromo- and -iodophosphate(III) Ion (pages 935–936)

      Priv.-Doz. Dr. William S. Sheldrick, Dipl.-Chem. Franz Zwaschka and Prof. Dr. Alfred Schmidpeter

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909351

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      The first phosphorus(III) compounds found to have coordination number 5 are the crown ether-alkali metal salts NaP(CN)3X, X = Br, I. A pseudo-octachedral lignad geometry is attained by dimerization of the anion.

    4. Novel, Highly Stereoselective Rearrangements of Chiral Dihydropyranones (pages 936–938)

      Prof. Dr. Frieder W. Lichtenthaler, Dr. Shigeru Nishiyama and Dipl.-Ing. Pan Jarglis

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909361

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      Important chiral synthons have been found in the dihydropyranones of types (1) and (3) derived from sugars. Enediolones (3) can be prepared by new, high-yield methods. Particular interest attaches to the rearrangement (3)[RIGHTWARDS ARROW](2); transfer of chirality takes place from one side of the ring to the other.

    5. Model System for the Electrochemical Reduction of the Carbon-Halogen Bond (pages 938–939)

      Priv.-Doz. Dr. Andreas Merz and Robert Tomahogh

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909381

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      All Postulated intermediated (2) of electrochemical reduction of the aryl halide(1), X[DOUBLE BOND]F, Cl, Br, are stable and can be directly observed: the anion (2a), ˆ[DOUBLE BOND]⊖, and the radical (2b), ˆ[DOUBLE BOND]⊙, and also the cation (2c), ˆ[DOUBLE BOND]⊕. The reduction-oxidation cycle can be traversed repeatedly.

    6. Direct Removal of Functional Groups by Catalytic Hydrogenolysis (pages 939–940)

      Dr. Wilhelm F. Maier, Dr. Peter Grubmüller, Dipl.-Ing. Irina Thies, Peter M. Stein, Prof. Dr. M. Anthony McKervey and Prof. Dr. Paul von Ragué Schleyer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909391

      Transformation of derivatives into the parent hydrocarbon by conventional methods often requires several steps and frequently gives poor yields. The direct removal of functional groups by catalytic (30% Ni/Al2O3) hydrogenolysis is demonstrated for adamantane derivatives; the procedure is suitable for number ous groups, yields are excellent, and the reaction can sometimes be controlled by change in temperature.

    7. (Bromoacetylmethylene)triphenylphosphorane— A Novel Cyclopentannelating Agent (pages 940–941)

      Dr. Hans-Josef Altenbach

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909401

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      A new reagent for producing five-membered rings is the known title compound (1). As an electrophilic C3 synthon it permits, via an intramolecular Wittig reaction, synthesis of cyclopentanes and of bicyclic and spiro compounds with cyclopentane partial structures.

    8. Dithiiranes and Thiosulfines as Reactive Intermediates (pages 941–942)

      Lektor fil. lic. Alexander Senning

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909411

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      The intermediacy of the

      CSS ring and/or its

      isomer appears likely from new experiments: reaction of (1) with morpholine leads via the unstable α-chloroalkyldisulfanes and the dithio esters (4) to stable products. (2)/(3) has not yet been trapped (R1,R2[DOUBLE BOND]CI; R1[DOUBLE BOND]PhS, R2[DOUBLE BOND]Tos).

    9. Directed Synthesis of the Trimeric Isoadenylate A2′p5′A2′p5′A (pages 942–943)

      Priv.-Doz. Dr. Joachim Engels and Ute Krahmer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909421

      New impetus for virus therapy should come from the isolation of an isoadenylate with “unnatural” 2′-5′ linkage from interferon-treated cells. This effector molecule, the title compound, has now been synthesized on a gram scale from inexpensive adenosine.

    10. Detection of Heavy Metal Ions by ESR Spectroscopy (pages 943–944)

      Prof. Dr. Hartmut B. Stegmann, Martin Schnabel and Prof. Dr. Klaus Scheffler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909431

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      The analytical application of ESR spectroscopy could acquire general importance. The hydroquinone (1) is suitable for complexation of the heavy metals to be detected. The complexes of (1) with Pb2+,Zn2+, and Cd2+ “extracted” from the aqueous phase were oxidized to paramagnetic π-systems and determined by ESR spectroscopy.

    11. Structure and Reactions of Methylenesulfur Tetrafluoride (pages 944–945)

      Prof. Dr. Hans Bock, Prof. James E. Boggs, Dipl.-Chem. Gert Kleemann, Dr. Dieter Lentz, Prof. Dr. Heinz Oberhammer, Dipl.-Chem. Eva Maria Peters, Prof.-Doz. Dr. Konrad Seppelt, Prof. Dr. Arndt Simon and Dr. Bahman Solouki

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909441

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      In the trigonal-bipyramidal species H2C[DOUBLE BOND]SF4(1) the H atoms are located in the plane of the axial F atoms (low-temperature crystal structure analysis, electron diffraction). The PE spectrum confirms that the resonance structure having a double bond has greater weight than in other ylides. (1) is exceptionally stable thermally, but highly reactive (addition to the polar C[DOUBLE BOND]S bond, CH2 transfer).

    12. 1,8a-Dihydroindolizines as Components of Novel Photochromic Systems (pages 945–946)

      Dipl.-Chem. G. Hauck and Prof. Dr. H. Dürr

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909451

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      Topical interest in photochromic systems is due in part to their application in silver-free photography, in data display technology, and possibly even in solar energy storage. The new system (1)⇌(2) is readily accessible and open to wide structural variation.

    13. 8,16-Methano[2.2]metacyclophane-1,9-diene. A Valence Isomer of 10b,10c-Methano-cis-10b, 10c-dihydropyrene (pages 946–947)

      Dr. Kazuhiro Nakasuji, Masanori Katada and Prof. Dr. Ichiro Murata

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909461

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      Laws governing the valence isomerization of polycyclic hydrocarbons have hardly been recognized so far; surprisingly, the new system (2), unlike (1), exists only as the “methano” isomer. The “cyclopropanetetrayl” isomer of (2) is postulated as intermediate in rearrangements.

    14. Synthesis and Reactions of Diazoacetyl Chloride—Detection of Diazoketene (pages 947–948)

      Prof. Dr. Hans Jürgen Bestmann and Dr. Fouad M. Soliman

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909471

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      Reaction of phosgene with diazomethane in the molar ratio 1:2 permitted the first synthesis of diazoacetyl chloride (3). Compound (3) decomposes only slowly below 0°C and is an excellent diazoacetylation reagent. The long-sought diazoketene N2C[DOUBLE BOND]C[DOUBLE BOND]O could be generated in solution from (3) and diazbicyclooctane.

    15. Synthesis and Structural Dynamics of Bis(cyclopentadienyl)phosphanepalladium Complexes (pages 948–949)

      Prof. Dr. Helmut Werner and Dipl.-Chem. Hans-Jürgen Kraus

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909481

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      A step on the way to palladocene could be the reaction shown below. The isolable compounds (1), L[DOUBLE BOND]PMe3, P(iPr)3, PPh3, show a single sharp singlet for all ten cyclopentadienyl protons in the NMR spectrum. A fluxional structure, at least in solution, is deduced from the temperature dependence of the spectrum.

    16. New Pathways to Trinuclear Complexes—Structure of the Tetra-decker Sandwich Complex Bis(η-thiadiborolenecobalt-μ,η-thiadiborolene)iron (pages 949–950)

      Prof. Dr. Walter Siebert, Dr. Wilfried Rothermel, Dipl.-Chem. Christian Böhle, Priv.-Doz. Dr. Carl Krüger and Dr. David J. Brauer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909491

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      Cleavage of triple-decker compounds with cyclopentadienide leads to anionic mononuclear complexes, which react to form trinuclear complexes. Thus the hitherto relatively inaccessible compound [(1)·Co·(1)·Fe·(1)·Co·(1)] has been obtained in 29% yield from [(1)·Co·(1)·Co·(1)] via [(1)·Co·(1)]. X-ray structure analysis confirmed the proposed tetra-decker geometry.

    17. A Stable 2-Adamantyl Cation in the Gas Phase (pages 950–951)

      Dipl.-Chem. Chrysostomos Wesdemiotis, Marita Schilling and Prof. Dr. Helmut Schwarz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909501

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      Adamantyl cations play a key role in carbocation chemistry. Only the 1-adamantyl cation (1) was previously known. It has now been shown by collision activation mass spectrometry that different cations arise from 1- and 2- adamantyl bromide. Structural assignment of (2) is supported by deuteration experiments.

    18. Ion Cyclotron Resonance Studies on tert-Butyl, 2-Norbornyl, and 1- and 2-Adamantyl Cations (pages 951–952)

      Dr. Raymond Houriet and Prof. Dr. Helmut Schwarz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909511

      The discussion about “classical”/“nonclassical”cations continues. ICR studies show that the 1-adamantyl cation is certainly not exceptionally stabilized (as has been repeatedly suspected) and that the energy of the 2-adamantyl cation differs by only 4 kcal/mol instead the expected amount of 16 kcal/mol. The analogy with the controversial 2-norbornyl cation/2-methyl-2-norbornyl cation system cannot be overlooked.

    19. Adamantene in the Gas Phase (pages 952–953)

      Prof. Dr. Helmut Schwarz, Prof. Dr. Manfred T. Reetz, Dr. Wilhelm F. Maier, Dipl.-Chem. Chrysostomos Wesdemiotis, Dipl.-Chem. Ioannis Chatziiosifidis and Marita Schilling

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909521

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      Adamentene (2), the “anti-Bredt compound” par excellence, has formerly only been detected by trapping experiments. It has now been generated as the neutral molecule in the mass spectrometer by unimolecular fragmentation of the radical cation (1), R[DOUBLE BOND]H or D, at ca. 10−6 torr. This observation was confirmed by comparison with the decomposition of the tert-butyl and cyclohexyl analogs of (1) and by peak shape analyses.

    20. Synthesis of a Platinum Complex with a Derivative of Monomeric Metathiophosphoric Acid as η2-Ligand (pages 953–954)

      Prof. Dr. Otto J. Scherer and Dipl.-Chem. Herbert Jungmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909531

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      The first complex to contain a π-bonded metathiophosphoric derivative has been prepared from R3C(SiR3)N[BOND]P([DOUBLE BOND]S)[DOUBLE BOND]NCR3 and L2Pt(C2H4). The two (CH3)3C groups are equivalent at room temperature; structure (a) was confirmed by X-ray methods. Its dynamic behavior at low temperature can be explained by participation of form (b) with pentacoordinated silicon (R = CH3, L = PPh3).

    21. Preparation of Stable Vinylketenes by Metal Complex-Induced Olefination and Carbonylation of Alkynes (pages 954–955)

      Dr. Karl Heinz Dötz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909541

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      The first vinylketenes stable under normal conditions, the bis(trimethylsilyl) compound (1) and its (arene-)Cr(CO)3 derivative, have been synthesized from a carbenecarbonyl-chromium complex and bis(trimethylsilyl)acetylene. Compound (1) has the s-trans conformation in the crystal.

    22. The Homologous Series of Cyclic Polysilanes from (Me2Si)5 to (Me2Si)35 (pages 955–956)

      Lawrence F. Brough, Dr. Koichi Matsumura and Prof. Dr. Robert West

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909551

      Permethylsilicon rings having 5 through 35 members arise on slow addition of Me2SiCl2 to Na/K alloy in boiling tetrahydrofuran. After removal of the major products (Me2Si)5 and (Me2Si)6 (recrystallization and fractional sublimation) the cyclic polysilanes can be detected by high pressure liquid chromatography.

    23. One-Pot Syntheses of α-Ferrocenylalkylamines (pages 956–957)

      Dipl.-Chem. Rudolf Herrmann and Prof. Dr. Ivar Ugi

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909561

      In order to carry out asymmetric peptide syntheses with 1-ferrocenyl-2-methylpropylamine on a large scale a convenient entry to this amine and similar compounds has been developed. One-pot syntheses in the trichloroacetic acid/fluorosulfuric acid solvent proved favorable(FcH = ferrocene).

      • equation image
    24. α,β-Unsaturated Carbonyl Compounds with Sterically Protected Carbonyl Groups—Enforced a3versus a1 Reactivity (pages 957–958)

      Prof. Dr. Dieter Seebach and Dipl.-Chem. Rita Locher

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909571

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      A shift in the reactivity of α,β-unsaturated carbonyl compounds can be accomplished by steric protection of the carbonyl group. Thus (1) reacts with organolithium exclusively at C-3 to give Michael adducts (2) which can be cleaved to form carboxylic acid derivatives.

    25. Chiral Reagents from Tartaric Acid—1-Benzyloxy-3,4-epoxy-2-butanol, a Versatile Intermediate for the Synthesis of Enantiomers (pages 958–960)

      Dipl.-Chem. Ernst Hungerbühler, Prof. Dr. Dieter Seebach and Dipl. sc. nat. Daniel Wasmuth

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909581

      Thumbnail image of graphical abstract

      As a “source of chirality”, tartaric acid has the advantages of ready accessibility in both enantiomeric forms and of reasonable price. The highly promising chiral epoxy alcohols (1) and (2) have been prepared from natural (R,R)-tartaric acid, and the mirror-image products from(S,S)-tartaric acid.

    26. The μ3-(η32O) Bridge—A Novel Mode of Coordination in the Structural Chemistry of Carbonylmetal Compounds (pages 960–962)

      Prof. Dr. Wolfgang A. Herrmann, Prof. Dr. Manfred L. Ziegler, Dr. Klaus Weidenhammer and Helmut Biersack

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909601

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      The first carbonylniobium cluster, and also the first example of a compound with end-on and doubly side-on coordinated CO ligands [type (1)] has been obtained by the action of sunlight on the readily accessible complex (2). The structure of (3) has been confirmed by X-ray structure analysis.

      • equation image
    27. 1,4-Dihydro-1,4-diazocine and N,N′-Disubstitution Products—A Rational Synthesis (pages 962–964)

      Dr. Hans-Josef Altenbach, Dipl.-Chem. Hartmut Stegelmeier, Dipl.-Chem. Monika Wilhelm, Burkhard Voss, Dr. Johann Lex and Prof. Dr. Emanuel Vogel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909621

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      Rings having 10 delocalizable electrons are of interest as potentially aromatic compounds. The unsubstituted 1,4-dihydro-1,4-diazocine (1) has now been prepared by two independent syntheses. Some N,N′-disubstituted derivatives of this ring system were already known. On the basis of its chemical behavior, spectra, and planar structure (confirmed by X-ray structure analysis), (1) is to be regarded as a 10π aromatic species. No prototropic shift to give (2) or (3) is observed. The character of the N,N′-disubstituted derivatives (4) is critically dependent upon the substituents.

    28. 1,4-Dihydro-1,4-diazocine; N-Substitution and Structure (“Aromaticity”) (pages 964–965)

      Dr. Manfred Breuninger, Dr. Bernd Gallenkamp, Dipl.-Chem. Klaus-Helmut Müller, Prof. Dr. Hans Fritz, Prof. Dr. Horst Prinzbach, Dr. John J. Daly and Peter Schönholzer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909641

      Thumbnail image of graphical abstract

      Rings having 10 delocalizable electrons are of interest as potentially aromatic compounds. The unsubstituted 1,4-dihydro-1,4-diazocine (1) has now been prepared by two independent syntheses. Some N,N′-disubstituted derivatives of this ring system were already known. On the basis of its chemical behavior, spectra, and planar structure (confirmed by X-ray structure analysis), (1) is to be regarded as a 10π aromatic species. No prototropic shift to give (2) or (3) is observed. The character of the N,N′-disubstituted derivatives (4) is critically dependent upon the substituents.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Author Index
    6. Subject Index
  4. Author Index

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Author Index
    6. Subject Index
    1. Author Index (pages 967–970)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909671

  5. Subject Index

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Author Index
    6. Subject Index
    1. Subject Index (pages 971–981)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197909711

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