Angewandte Chemie International Edition in English

Cover image for Vol. 16 Issue 12

December 1977

Volume 16, Issue 12

Pages 807–898

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 12/1977)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708071

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 12/1977)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708072

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    6. Author Index
    7. Subject Index
    1. The Selectivity of Chemical Reactions Disguised by Diffusion. Part I: Chemical Selectivity Disguised by Mixing (pages 807–817)

      Prof. Dr. Paul Rys

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708073

      Thumbnail image of graphical abstract

      The influence of mixing effects on the product distribution in competitive consecutive and parallel reactions can be of importance. A mixing-reaction model has been used for deducing criteria providing information about such an influence.

    2. Titanium Tetrachloride in Organic Synthesis [New synthetic methods (21)] (pages 817–826)

      Prof. Dr. Teruaki Mukaiyama

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708171

      Thumbnail image of graphical abstract

      Syntheses in acid solution can be accomplished with the aid of TiCl4. Examples are transformations of functional groups and CC coupling.

    3. Spontaneous Alternating Copolymerization via Zwitterion Intermediates (pages 826–835)

      Prof. Dr. Takeo Saegusa

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708261

      Thumbnail image of graphical abstract

      A new type of copolymerization is based on the spontaneous reaction of nucleophilic (MN) and electrophilic monomers (ME) to form zwitterions +MN—Mmath image. No catalyst is required.

    4. Thermal and Photochemical Cycloelimination of Nitrogen (pages 835–851)

      Prof. Dr. Herbert Meier and Doz. Dr. Klaus-Peter Zeller

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708351

      Thumbnail image of graphical abstract

      The elimination of N2 from cyclic azo compounds leads to primary fragments which can stabilize in numerous ways. This provides a method of synthesizing, e.g. small carbo- and heterocyclic compounds as well as strained bi- and polycyclic species.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    6. Author Index
    7. Subject Index
    1. Quantitative Trace Analysis of Metals by Field Desorption Mass Spectrometry (pages 852–853)

      Dr. Wolf Dieter Lehmann and Dr. Hans-Rolf Schulten

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708521

      The quantitative determination of 6Li and 7Li in Rhine water and determination of the isotopic distribution in some commercial Li salts have been performed by FD mass spectrometry in combination with a multi-channel analyzer. Surprisingly, the isotopic distribution in the Li salts deviates from the mean natural abundance. In contrast, the natural distribution is found in Rhine water. Using 6Li-enriched LiF as standard, 6Li and 7Li can be determined quantitatively by the method of isotopic dilution (total error 5%).

    2. Functional Vinyl Carbanions—Deprotonation of β-(1-Pyrrolidinyl)acrylonitrile (pages 853–854)

      Prof. Dr. Richard R. Schmidt and Dipl.-Chem. Jörg Talbiersky

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708531

      Thumbnail image of graphical abstract

      Selective electrophilic reactions at the α- or β-position of β-(1-pyrrolidinyl)acrylonitrile (1), NR2 = pyrrolidinyl, can be accomplished in many cases by lithiation of (1) at −113 or −76°C and subsequent reaction with the electrophile.

    3. A New Method for the Introduction of Trifluoromethyl Groups (pages 854–855)

      Dipl.-Chem. Peter Gölitz and Prof. Dr. Armin de Meijere

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708541

      The first general trifluoromethylation of alkanes has now been discovered. The CF3 substituent provides a means of making unstable molecules isolable; in addition, CF3 derivatives often exhibit enhanced pharmacological activity.

      • equation image
    4. Oxidation and Reduction of Methylthio-Substituted π-Systems and the Electron Distribution in Their Radical Ions (pages 855–856)

      Prof. Dr. Hans Bock and Dipl.-Chem. Georg Brähler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708551

      Thumbnail image of graphical abstract

      The radical anion M•⊖ and the radical cation M•⊕ have so far both been detected for few molecules M. Methylthio-substituted π-systems such as (1) represent a new type of such molecules. Comparison of the calculated charge distributions for M, M•⊖, and M•⊕ with the experimental spin densities ρ and ρ is of topical interest.

    5. Ba3As14, The First Compound with the Cluster Anion Asmath image (page 857)

      Dr. Walter Schmettow and Prof. Dr. Hans Georg von Schnering

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708571

      Thumbnail image of graphical abstract

      A cluster of seven arsenic atoms is found in the Asmath image anion. It occurs in Ba3As14 which is formed from Ba and As at 1000 to 1100 K. The Pmath image and Sbmath image anions are already known.

    6. (η-Cyclopentadienyl)cobalt-μ-(η-diborolenyl)(η-cyclopentadienyl)iron—A Triple Decker Sandwich Complex Containing Two Different Metals (pages 857–858)

      Prof. Dr. Walter Siebert and Dipl.-Chem. Manfred Bochmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708572

      Thumbnail image of graphical abstract

      The first mixed metal triple decker sandwich complex(1), a diamagnetic compound, has now been synthesized. (1) is formed by simultaneous reaction of 1,3,4,5-tetraethyl-2-methyl-1,3-diborolene with CpCo(CO)2 and [CpFe(CO)2]2.

    7. A New Coordination Form of Acetylacetone (pages 858–859)

      Dipl.-Chem. Joachim von Seyerl, Dietmar Neugebauer and Prof. Dr. Gottfried Huttner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708581

      Thumbnail image of graphical abstract

      In the novel acetylacetone complex(1) the ligand is coordinated as the dienediolate. All previously reported complexes contain the acetylacetone as enolate, β-diketone, π-ligand, or σ-organyl group.

    8. Addition Compounds with Polymeric Chromium(II)-Schiff Base Complexes (pages 859–860)

      Prof. Dr. Wolfgang Sawodny and Dipl.-Chem. Manfred Riederer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708591

      Thumbnail image of graphical abstract

      Highly stable complexes of Schiff bases and chromium(II), palladium(II), or platinum(II) have now been synthesized. Such a complex is the Cr2+ compound (2a). It can form addition compounds with molecules such as CH3OH, pyridine, or cyclohexane. Complexes of type (2) containing Pd2+ or Pt2+ and R = e.g.[BOND](CH2)x[BOND], x = 2–8, 10, 12 are accessible from (1) and K2PdCl4 or K2PtCl4 in DMF/NaOAc. They can also intercalate organic molecules.

    9. Palladium(II) and Platinum(II) Complexes with Polymeric Schiff Base Ligands (pages 860–861)

      Dipl.-Chem. Manfred Riederer, Erna Urban and Prof. Dr. Wolfgang Sawodny

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708601

      Thumbnail image of graphical abstract

      Highly stable complexes of Schiff bases and chromium(II), palladium(II), or platinum(II) have now been synthesized. Such a complex is the Cr2+ compound (2a). It can form addition compounds with molecules such as CH3OH, pyridine, or cyclohexane. Complexes of type (2) containing Pd2+ or Pt2+ and R = e.g.[BOND](CH2)x[BOND], x = 2–8, 10, 12 are accessible from (1) and K2PdCl4 or K2PtCl4 in DMF/NaOAc. They can also intercalate organic molecules.

    10. The “Zip” Reaction: A New Method for Ring Expansion; Synthesis of 17- and 21- Membered Polyaminolactams (pages 861–862)

      Dipl.-Chem. Urs Kramer, Armin Guggisberg, Prof. Dr. Manfred Hesse and Prof. Dr. Hans Schmid

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708611

      Thumbnail image of graphical abstract

      Large nitrogen-containing rings are preparable in very good yields by the “zip” reaction. Thus the 17-membered lactam can be transformed, as the Na salt, into (2) by reaction with acrylonitrile and then with H2/Pt; in the presence of K[NH(CH2)3NH2], (2) rearranges with ring expansion to (3). Compound (1) was obtained analogously from the 13-membered lactam.

    11. A Stable Acyclic Alkoxyhalosulfurane: Chlorotris(2,2,2-trifluoro-1-trifluoromethylethoxy)sulfurane (page 862)

      Dr. Gerd-Volker Röschenthaler

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708621

      Alkoxysulfuranes—compounds containing a tetracoordinated sulfur(IV)atom—are important intermediates in synthetic organic chemistry. The first open-chain chloroalkoxysulfurance has now been prepared. Surprisingly, it is able to alkoxylate

      • equation image
    12. Carbonyl Olefination with (Triphenylstannyl)methyllithium (pages 862–863)

      Prof. Dr. Thomas Kauffmann, Dipl.-Chem. Reinhard Kriegesmann and Annegret Woltermann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708622

      A modified alternative to the Wittig reaction utilizes (triphenylstannyl)methyllithium. Yields are good; the alcohol does not have to be isolated.

      • equation image
    13. Four-Membered Phosphorus-Nitrogen-Metal Heterocycles with Zwitterionic Structure (pages 864–865)

      Priv.-Doz. Dr. Edgar Niecke, Dipl.-Chem. Rainer Kröher and Dr. Siegfried Pohl

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708641

      Thumbnail image of graphical abstract

      Novel cyclic zwitterions of type (1), R[DOUBLE BOND]SiMe3, EXn[DOUBLE BOND]SnCl2, AlCl3, FeCl3, TiCl4, NbCl5 have four-membered rings with positively charged P and negatively charged metal atom. The structure of (1), EXn−1[DOUBLE BOND]TiCl3, was confirmed by X-ray analysis.

    14. Intramolecular Oxidative Addition of Azopyridine to Phosphorus(III) (pages 865–866)

      Prof. Dr. Alfred Schmidpeter and Dipl.-Chem. Josef Helmut Weinmaier

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708651

      Thumbnail image of graphical abstract

      Not only metal ions but also phosphorus(III) react with the pyridylazo compound “PAN” (1), an indicator for complexometric titrations. Intramolecular redox reaction affords a bicyclic phosphorane.

    15. Stable Thiocarbonyl Ylides (pages 866–867)

      Dr. Kazuhiro Nakasuji, Keitaro Nishino, Prof. Dr. Ichiro Murata, Dr. Hisanobu Ogoshi and Prof. Dr. Zen'ichi Yoshida

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708661

      Thumbnail image of graphical abstract

      Are thiocarbonyl ylides of type (1) stabilized by participation of structure (2) in the ground state?(3), X[DOUBLE BOND]CN, Y[DOUBLE BOND]H, and (4), X[DOUBLE BOND]H, Y[DOUBLE BOND]CN, form stable crystals; 13C- and 1H-NMR spectra suggest localized negative charge and partial double bond character of the (C-1′)[BOND]S bond.

    16. Formation of Diazo Compounds on Decomposition of 2,3-Diazabicyclo[3.1.0]hex-2-enes:[3+2]-Cycloreversions (pages 867–869)

      Dr. Manfred Schneider and Bernd Csacsko

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708671

      Thumbnail image of graphical abstract

      The decomposition of bicyclic pyrazolines of type(1) has been elucidated: it proceeds via diazo compounds and carbenes. On direct UV irradiation of (1) in an NMR spectrometer rapid disappearance of the signals of (1) and the formation of (2) are observed. This is the first NMR identification of such an unstable diazo compound.

    17. Formation of the (Z,E)-1,3-Diphenylallyl Radical from the (Z,E)-1,3-Diphenylallyl Anion by Electron Transfer—Comparison of the Rotational Barriers of the Radical and the Anion (pages 869–870)

      Priv.-Doz. Dr. Gernot Boche and Dipl.-Chem. Dieter R. Schneider

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708691

      Thumbnail image of graphical abstract

      The (Z,E)-1,3-diphenylallyl radical has a very low rotational barrier, as demonstrated by the ratios of the yields of dimers. In contrast, the topologically identical anion is configurationally stable.

    18. Bis(η6-naphthalene)chromium(0) (pages 870–871)

      Prof. Dr. Christoph Elschenbroich and Reinhart Möckel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708701

      Thumbnail image of graphical abstract

      More than 20 years after bis(η-benzene)chromium(0) the higher homolog, naphthalene derivative (1), has now been prepared. It was synthesized by cocondensation of metal atom and ligand at −196°C. Neutral naphthalene complexes of this kind were formerly unknown.

    19. Octalene (pages 871–872)

      Prof. Dr. Emanuel Vogel, Dipl.-Chem. Hans-Volker Runzheimer, Dipl.-Chem. Frank Hogrefe, Dr. Bernd Baasner and Dr. Johann Lex

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708711

      Thumbnail image of graphical abstract

      The synthesis, structure, and properties of octalene are described for the first time. This [8]annuleno[8]annulene, accessible in many steps from a tetrahydronaphthalene, is a lemon yellow hydrocarbon that is very air-sensitive. Independent structural proof was obtained by crystal structure analysis of a triazolinedione adduct. Examination of the 13C-NMR spectra at +120, +25, and −150°C ruled out the form with a central double bond and the aromatic form. The temperature dependence of the spectrum indicates mutually independent inversions of the cyclooctatetraene and the cyclooctatriene fragments. The peripheral π-bonds undergo shifts above about 80°C. The transition state is planar.

    20. Configuration, Conformation, and Dynamics of Octalene (pages 872–874)

      Prof. Dr. Jean F. M. Oth, Priv.-Doz. Dr. Klaus Müllen, Dipl.-Chem. Hans-Volker Runzheimer, Peter Mues and Prof. Dr. Emanuel Vogel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708721

      Thumbnail image of graphical abstract

      The synthesis, structure, and properties of octalene are described for the first time. This [8]annuleno[8]annulene, accessible in many steps from a tetrahydronaphthalene, is a lemon yellow hydrocarbon that is very air-sensitive. Independent structural proof was obtained by crystal structure analysis of a triazolinedione adduct. Examination of the 13C-NMR spectra at +120, +25, and −150°C ruled out the form with a central double bond and the aromatic form. The temperature dependence of the spectrum indicates mutually independent inversions of the cyclooctatetraene and the cyclooctatriene fragments. The peripheral π-bonds undergo shifts above about 80°C. The transition state is planar.

    21. Observation of a Linear Relationship Between Thermal Stability and Strain Energy of Alkanes (pages 875–876)

      Prof. Dr. Christoph Rüchardt, Dr. Hans-Dieter Beckhaus, Dr. Goetz Hellmann, Dipl.-Chem. Siegried Weiner and Dipl.-Chem. Robert Winiker

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708751

      Thumbnail image of graphical abstract

      The differing stability of alkanes between 150 and 700°C has now been quantitatively interpreted. A linear relation exists between the free energy of activation ΔG of thermolysis of many alkanes and their strain energy as determined by force field calculations.

    22. A New Lactone Synthesis (pages 876–877)

      Prof. Dr. Helmut Vorbrüggen and Konrad Krolikiewicz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708761

      Thumbnail image of graphical abstract

      The total synthesis of macrolides and other lactones can utilize a new method of ring closure between a hydroxy and carboxy group. All the reagents used are volatile.

    23. Preparation and Reactions of a Cyclic Phosphaallene Ylide (pages 877–878)

      Prof. Dr. Hans Jürgen Bestmann, Dipl.-Chem. Kurt Roth and Priv.-Doz. Dr. Rolf W. Saalfrank

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708771

      Thumbnail image of graphical abstract

      The structureal unit

      is present as part of a ring in compound (1). This first cyclic phosphaallene ylide has now been synthesized and isolated in crystalline form. It can be stored for a limited period if cooled.

    24. Simple Stereoselective Synthesis of Eburnamonine (pages 878–879)

      Friederike Klatte, Dipl.-Chem. Ulrich Rosentreter and Prof. Dr. Ekkehard Winterfeldt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708781

      Thumbnail image of graphical abstract

      Regioselective ring opening of the cyclopropane derivative(1), R[DOUBLE BOND]C2H5, is the key step in the synthesis of the vincamine alkaloid eburnamonine (2). The cis-D,C linkage in (2) represents the crucial stereochemical problem in this series.

    25. Isolation of Acyl Thioacyl Sulfides (pages 879–880)

      Prof. Dr. Shinzi Kato, Katsumi Sugino, Masatoshi Yamada, Tomonori Katada and Prof. Dr. Masateru Mizuta

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708791

      Thumbnail image of graphical abstract

      Mixed thioanhydrides of dithiocarboxylic acids and acetic acid have now been obtained for the first time. Their synthesis was accomplished by reaction of Na or piperidinium dithiocarboxylates with acetyl chloride.

    26. The First Reaction of the N2 Ligand with Bases; Reduction of Coordinated Dinitrogen by Nucleophilic Attack (pages 880–881)

      Professor Dr. Dieter Sellmann and Dr. Woldemar Weiss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708801

      Thumbnail image of graphical abstract

      Nitrogen bound to a transition metal can be reduced in a fundamentally new way by base addition with retention of the N2-coordinating center; both reaction steps can be observed individually.

    27. Catalyst-Dependent Product Distribution in the Reaction of 1-Hexene with a Hydrosilane and Carbon Monoxide (pages 881–882)

      Yoshio Seki, Prof. Dr. Shinji Murai, Akihiko Hidaka and Prof. Dr. Noboru Sonoda

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708811

      Thumbnail image of graphical abstract

      The regio- and stereoselectivity of reaction as well as the activity of various catalysts show a close relationship to exist between the hydroformylation of olefins and their reaction with hydrosilanes and CO.

    28. Comment on the Publication Entitled “Synthesis of a Stable 1,3,4-Dioxazolidine” (page 882)

      Prof. Dr. Gerwalt Zinner and Helmut Blass

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708821

      Comment on the Publication “Synthesis of a Stable 1,3,4-Dioxazolidine”

  3. Book Reviews

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

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    6. Author Index
    7. Subject Index
    1. You have free access to this content
      Corrigendum (page 884)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708841

  5. Author Index

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    6. Author Index
    7. Subject Index
    1. Author Index 1977 (pages 885–888)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708851

  6. Subject Index

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    6. Author Index
    7. Subject Index
    1. Subject Index 1977 (pages 889–898)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197708891

SEARCH

SEARCH BY CITATION