Angewandte Chemie International Edition in English

Cover image for Vol. 19 Issue 7

July 1980

Volume 19, Issue 7

Pages 495–574

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 7/1980)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198004951

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 7/1980)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198004952

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. The Principle of Minimum Chemical Distance (PMCD) (pages 495–505)

      Dr. Clemens Jochum, Dr. Johann Gasteiger and Prof. Dr. Ivar Ugi

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198004953

      Thumbnail image of graphical abstract

      The planning of syntheses, structural analysis, and the determination of reaction mechanisms are just three of the topics to which the PMCD can be applied, sometimes with resounding success. With the aid of this principle, which is based on the algebraic theory of constitutional chemistry, many questions can be formulated as optimization problems which can generally be solved in less than one second by computer.

    2. High-Resolution Transmission Electron Microscopy Re-examined as a Tool in Solid State Chemistry (pages 505–520)

      Prof. Dr. Reginald Gruehn and Dr. Wilhelm Mertin

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005051

      Thumbnail image of graphical abstract

      The lattice imaging of crystal structures in an electron microscope is now approaching atomic resolution. This method can detect very slight defects, faults in the stacking sequence of structural groups or atom layers, and even structural defects in regions smaller than a unit cell. The structural principle of even the very smallest ordered regions can be determined when X-ray structure analysis fails.

    3. Alkali Metal-Transition Metal π-Complexes (pages 520–537)

      Priv.-Doz. Dr. Klaus Jonas and Priv.-Doz. Dr. Carl Krüger

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005201

      Thumbnail image of graphical abstract

      Compounds of alkali metals, transition metals, olefins or N2 (side-on), and nothing (or very little) else are themselves surprising enough; in addition, some of these novel complexes exhibit remarkable properties. Crystal structure analyses should provide an indication of the bonding in these compounds. (Example: [Li(TMEDA)]2Ni(CDT).)

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Electrochemical Oxidation of Dicarbene Complexes of the Type (Carbene)2MoL(CO)3: Interconversion Among Three Isomers via Electrochemical Redox Processes (pages 538–540)

      Prof. Dr. Reuben D. Rieke, Hiroyuki Kojima and Dr. Karl Öfele

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005381

      Thumbnail image of graphical abstract

      Unusual isomerizations have been observed in the new dicarbenemetal complexs (1): the three isomers undergo mutual interconversion via electrochemical redox processes (L = cyclohexyl isocyanide, PEt3, PPh3).

    2. A Phlorizin Polymer as Affinity Gel for Sugar-Binding Proteins (pages 540–541)

      Dr. Jiann-Trzuo Lin and Prof. Dr. Rolf Kinne

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005401

      Thumbnail image of graphical abstract

      Affinity chromatography of sugar-binding proteins can be accomplished on a gel obtained from the natural β-glycoside (1) in which the aglucone moiety has been cross-linked while the sugar residue remains intact.

    3. Collision Induced Fragmentation of Alkylideneammonium Ions (pages 541–542)

      Dr. Hans J. Veith

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005411

      Thumbnail image of graphical abstract

      Mass spectrometric analysis of alkylideneam-monium ions such as (1) and (2) was formerly impossible. A combination of field desorption (FD) and collision activation (CA) now permits generation of intact ions from the salts and fragmentation of these ions.

    4. Base-Catalyzed Conversion of an Equatorial into an Axial Methoxycarbonyl Group Due to a 1,5-Long-Range Substituent Effect (page 543)

      Prof. Raphael Mechoulam, Dr. Naftali Lander, Dr. Ilana Tamir, Dr. Zvi Ben-Zvi and Yosef Kimmel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005431

      Thumbnail image of graphical abstract

      The unusual transformation of an equatorial CO2Me group into an axial one has been observed in the hexahydrocannabinol skeleton [(2a) [RIGHTWARDS ARROW] (1a), R = Ac]. In the methyl ethers, however, the expected reaction takes place [(1b) [RIGHTWARDS ARROW] (2b), R = Me]. The epimerization of (2a) in the presence of strong bases is attributed to the potential phenolate ion situated five carbon atoms away.

    5. 1,4-Dihydro-1,4-bis(dicyanomethylene)triptycenes. Synthesis and Intramolecular Charge-Transfer Interaction (pages 543–545)

      Prof. Dr. Kimiaki Yamamura, Prof. Dr. Tomoo Nakazawa and Prof. Dr. Ichiro Murata

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005432

      Thumbnail image of graphical abstract

      Intramolecular CT interaction in spite of nonparallel donor and acceptor units occurs in (1), Y = H. OCH3. The interaction in (1) is even stronger than in (2), which has parallel donor and acceptor units.

    6. Synthesis and Intramolecular Charge-Transfer Interaction in 1,4-Dihydro-1,4-ethanobenzotropylium Tetrafluoroborate (pages 545–546)

      Prof. Dr. Tomoo Nakazawa, Yoshihide Niimoto, Keiji Kubo and Prof. Dr. Ichiro Murata

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005451

      Thumbnail image of graphical abstract

      In order to examine the conditions for intramolecular CT interaction between nonparallel donor and acceptor units, the tropylium salts (1) and (for comparison) (2) have been synthesized. Compound (1) shows strong CT interaction in an excited state; however, the stabilization of (1) (and of (2)) relative to the tropylium ion in the ground state is attributable to bridging.

    7. L-Gulose or D-gluco-Hexodialdose from D-Glucurono-6,3-lactone by Controlled Reductions (pages 546–547)

      Dr. Wilhelm V. Dahlhoff, Dipl.-Chem. Peter Idelmann and Prof. Dr. Roland Köster

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005461

      Thumbnail image of graphical abstract

      New reduction reactions with boranes in sugar chemistry permitted the first synthesis of anhydrous solid L-gulose (1) (with Et2BH). The same starting material can also yield anhydrous solid D-gluco-hexodialdose (2) (with 1. (EtBO)3 and 2. Et2BH).

    8. Pure D-Gulose from D-Gulono-1,4-lactone (pages 547–548)

      Prof. Dr. Roland Köster, Dipl.-Chem. Peter Idelmann and Dr. Wilhelm V. Dahlhoff

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005471

      Thumbnail image of graphical abstract

      The combined action of boranediyl protecting groups and reducing boranes permits the first preparation of pure, solid, anhydrous D-gulose (1). The three-step reaction is quantitative.

    9. Simple New Method for the Synthesis of 2-Deoxy-aldehydo-hexoses (pages 548–549)

      Dr. Wilhelm V. Dahlhoff and Prof. Dr. Roland Köster

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005481

      Thumbnail image of graphical abstract

      Open-chain 2-deoxyhexoses bearing difunctional ethylboranediyl protecting groups are accessible in a single step from the corresponding (cyclic) unprotected 2-deoxyhexoses. (1a) is in equilibrium with ≲20% of the 3,4:5,6-isomer; (2a) is accompained by ca. 15% of the 3,5:4,6-isomer. (The bold point symbolizes the

      group.)

    10. Absolute Configuration of the Cancerostatic S(–)-Isophosphamide (pages 549–550)

      Dr. Dorota A. Adamiak, Dr. Maira Gdaniec, Dr. Krzysztof Pankiewicz and Prof. Dr. Wojciech J. Stec

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005491

      Structure/activity relations in chiral drugs can only be studied if the absolute configuration is known. The levorotatory form of the cancerostatic isophos-phamide is shown by X-ray structure analysis to have the S configuration.

    11. Vesicles with a Monolayer, Redox-Active Membrane (pages 550–551)

      Dipl.-Chem. Ehrenfried Baumgartner and Prof. Dr. Jürgen-Hinrich Fuhrhop

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005501

      Thumbnail image of graphical abstract

      A membrane comprising a single layer of close-packed molecules occurs in vesicles that can be produced from the tetracation corresponding to (1). Reduction by dithionite leads merely to (1) since the ions cannot penetrate the hydrophobic membrane. It appears likely, however, that electrons and protons can be introduced into the membrane to drive energy-consuming processes.

    12. New Dinuclear Iridium(II) Complexes Arising by Oxidative Addition of I2 to [Ir2(μ-StBu)2 (CO)2L2] (pages 551–552)

      Prof. Jean-Jacques Bonnet, Dr. Philippe Kalck and Prof. René Poilblanc

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005511

      The small family of iridium (II) complexes has increased in size. In the case of (1), L = CO and L = PMe3, the reaction shown below leads to two isomers each, which do not interconvert. The product having L = PMe2Ph has been characterized by X-ray structure analysis.

      • equation image
    13. A Novel Proton-Ordered, Two-Dimensional Cross-linking of Water Molecules in Pyridine Trihydrate (pages 552–553)

      Prof. Dr. Dietrich Mootz and Dipl.-Chem. Hans-Georg Wussow

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005521

      The solid pyridine-water addition compound, hitherto regarded as a dihydrate, has now been shown by a new study of the pyridine-water melting diagram and complete X-ray structural analysis to be the trihydrate. Typical two-dimensional cross-linking of the water molecules gives annelated rings; protons not involved in these rings from H bonds to pyridine.

    14. A New Variant of the Amphoterism of Tin(II) Hydroxide: Sn(OH)2 as Stannio Complex Ligand (pages 553–554)

      Priv.-Doz. Dr. Wolf-Walther du Mont and Brigitte Neudert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005531

      A novel mode of fixing a transition metal to an amphoteric inorganic polymer has been accomplished in the complexes (2). Complexes having coordinative Sn[BOND]M bonds were formerly unknown. Sn(OH)2 is still highly associated in (2) (M = Cr, W; R = Ph, Me).

      • equation image
    15. Bis(di-tert-butylphosphino)tellurium(II): A Derivative of Phosphinous Anhydride Exhibiting Umpolung (pages 554–555)

      Priv.-Doz. Dr. Wolf-Walther du Mont

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005541

      The title compound (1)—obtained via the reaction shown below and independently from Na2 Te and tBu2PCl— is formed very readily. (1) is the first tellurium compound to contain only R2P substituents. Its reactions prompt us to consider the bonding in (1) and in other Te[BOND]P compounds.

      • equation image
    16. Ring-Strained Carbodiphosphoranes (pages 555–556)

      Prof. Dr. Hubert Schmidbaur, Dipl.-Chem. Thomas Costa, Dipl.-Chem. Beatrix Milewski-Mahrla and Dr. Ulrich Schubert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005551

      Thumbnail image of graphical abstract

      The first rings to contain the structural unit P[DOUBLE BOND]C[DOUBLE BOND]P have been obtained by reaction of Ph2PCH2PPH2 with Br(CH2)nBr (n = 2, 3, 4). The chemical properties and the bond lengths and angles in carbodiphosphorane with n = 2 are best described by the following formulation:

    17. Ph(Me3Si)C[DOUBLE BOND]P[BOND]Cl, the First P-Halofunctionalized Methylenephosphane (pages 556–557)

      Prof. Dr. Rolf Appel and Dipl.-Chem. Axel Westerhaus

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005561

      Thumbnail image of graphical abstract

      Valuable synthons—the acyclic P-chlorinated PIII compounds (2) having coordination number 2—are readily accessible from the dichlorophosphanes (1) with bases. Compound (2). R = Ph, R′ = SiMe3, might provide an entry to P[TRIPLE BOND]C triple bonds.

    18. Highly Stereoselective Aldol Condensation Using an Enantioselective Chiral Enolate (pages 557–558)

      Prof. Dr. Satoru Masamune, Dr. Sk. Asrof Ali, Dr. David L. Snitman and David S. Garvey

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005571

      Thumbnail image of graphical abstract

      The 3,4-stereochemistry of aldol adducts can now be controlled for the first time with the new, chiral, readily accessible enolate reagent (2); i.e. the chiral aldehyde (1) can be transformed both into 3,4-anti- and into the 3,4-syn-aldol adduct, (3) and (4), as major product. (2a) forms (3a) and (4a) in the ratio of 15:1, while (2b) leads to (3b) and (4b) in the ratio of 1:10.

    19. Outer Sphere Electron Transfer Reactions: A Novel Linear Relationship between the Selectivity and the Normal Potential of the Reducing Agent (pages 558–559)

      Dipl.-Chem. Hans-Michael Huck and Prof. Dr. Karl Wieghardt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005581

      Interesting consequences for new theoretical models might result from the novel relationship mentioned in the title, which has been found for electron transfer between two transition metal complexes (in the encounter complex). Equation (a) is an example. Previous theories failed to predict the observed selectivity.

      • equation image
    20. Biscarbyne Cluster by Alkyne Cleavage: A General Reaction (pages 559–561)

      John R. Fritch and Prof. Dr. K. Peter C. Vollhardt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005591

      Thumbnail image of graphical abstract

      Cleavage of the C[TRIPLE BOND]C bond by CpCo(CO)2 provides the most facile entry conceivable to biscarbyne clusters such as (1). In this reaction bis(trimethylsilyl)butadiyne and -hexatriyne form. inter alia, complexes with two cluster units. All these complexes are possibly suitable as models for H/D exchange reactions and hydroformylation.

    21. Gold(I)-Gold(I) Interactions. Tetrameric Gold(I) Dithioacetate (pages 561–562)

      Prof. Olivo Piovesana and Prof. Pier Francesco Zanazzi

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005611

      Thumbnail image of graphical abstract

      A rhombus of four gold atoms is present in the new complex [Au4(CH3CSS)4], which is characterized by short Au[BOND]Au contacts and extensive mixing of metal and ligand orbitals. (1) is formed from NaAuCl4 and CH3CSSH, and is obtained as red, air-stable crystals.

    22. Are α-Oxothioacyl Chlorides Formed in the Reaction of Methyl Ketones with Thionyl Chloride? (pages 563–564)

      Dr. Gunadi Adiwidjaja, Dipl.-Chem. Horst Günther and Prof. Dr. Jürgen Voss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005631

      The answer to the question posed in the title is no; thus, previous claims in the literature have to be corrected. Work in this field has led to the new class of O-alkyl α-oxothiocarboxylates.

      • equation image
    23. Acylated Ketenimines and Allenes from Oxazol-5(4H)-ones and Furan-2(3H)-ones (pages 564–566)

      Dipl.-Chem. Hans-Michael Berstermann, Dr. Raymond Harder, Dipl.-Chem. Hans-Wilhelm Winter and Prof. Dr. Curt Wentrup

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005641

      Thumbnail image of graphical abstract

      Surprising results are obtained on flash vacuum pyrolysis of the lactones (1) and similar heterocycles with a “CO2 partial structure”. Elimination of CO yields (unsaturated) ketones (2).

    24. Cyclic Carbodiimides in Nitrene Rearrangements (pages 566–567)

      Prof. Dr. Curt Wentrup, Dr. Célestin Thétaz, Dipl.-Chem. Enrico Tagliaferri, Prof. Dr. Hans Jörg Lindner, Brigitte Kitschke, Dipl.-Chem. Hans-Wilhelm Winter and Dr. Hans Peter Reisenauer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005661

      Thumbnail image of graphical abstract

      Convicing evidence for the first seven-membered cyclic carbodiimide(2) was obtained on rearrangement of the nitrenes (1) and (3) in the gas phase, in solution, and in an argon matrix. At 10 K (2) is stable and can be detected by IR spectroscopy.

    25. cis-/trans-Tris-[2.1.1]-σ-homobenzenes; Synthesis and Stereochemistry of [σ2 + σ2 + σ2]-Cycloreversions (pages 567–568)

      Prof. Dr. Horst Prinzbach, Dipl.-Chem. Hans-Peter Schal, Dr. Dieter Hunkler and Prof. Dr. Hans Fritz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005671

      Thumbnail image of graphical abstract

      Ring cleavage of the new cis-/trans-isomeric ketones (1) and (3) at 150 and 300°C leads via [σ2 + σ2 + σ2]-cycloreversion to the cyclodecatrienones (2) (100%) and (4) (88%) + (2) (5%), respectively. These reactions are impressive examples of the promotion of cooperative processes in tris-σ-homobenzenes.

    26. Ligand-Property Control in the Nickel(0)/Butadiene/P-Ligand Catalytic System: Dominance of “Steric” Factors in the Control of Oligomer Distribution (pages 569–570)

      Prof. Dr. Paul Heimbach, Dipl.-Chem. Joachim Kluth, Dr. Hartmut Schenkluhn and Dr. Bruno Weimann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005691

      Thumbnail image of graphical abstract

      The influence of ligands on the result of a metal-catalyzed reaction has been studied for the formation of dimers and trimers from butadiene with Ni0/PR3. Multilinear regression analysis showed the oligomer distribution to be largely dependent upon “steric” factors. Large and small apical angles favor cyclotri-merization, and increasing donor character has the same effect. (Su = substrate = butadiene, m = 0 or 1.)

    27. Ligand-Property Control in the Nickel(0)/Butadiene/P-Ligand Catalytic System: “Electronic” Factors in the Control of Cyclodimer Distribution (pages 570–571)

      Prof. Dr. Paul Heimbach, Dipl.-Chem. Joachim Kluth, Dr. Hartmut Schenkluhn and Dr. Bruno Weimann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005701

      Thumbnail image of graphical abstract

      The cyclodimer distribution in the Ni0/PR3-catalyzed oligomerization of butadiene depends upon “electronic” factors of the ligands. An opposing effect must also be considered, viz. a ligand-induced relative activation or inhibition of the product-forming reaction step. (VCH = vinylcyclohexane, COD = 1,5-cyclooctadiene, Su = substrate = butadiene, m = 0 or 1.)

    28. P4(N-i-C3H7)6, a P4X6 Molecule with and without Adamantane Structure (pages 571–572)

      Prof. Dr. Otto J. Scherer, Dipl.-Chem. Kurt Andres, Priv.-Doz. Dr. Carl Krüger, Dr. Yi-Hung Tsay and Dr. Gotthelf Wolmerhäser

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005711

      Thumbnail image of graphical abstract

      The first P4X6 molecule to have a cryptand structure, the title compound (1), is formed on thermolysis of a (P[BOND]NR)2 ring bearing Me3Si[BOND]NR and Cl as substituents. On prolonged heating, (1) assumes the adamantane structure, like all other P4X6 molecules.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Book Review: Radiotracers in Agricultural Chemistry. By M. F. L'Annunziata (page 573)

      Albert Wünsch

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005731

    2. Book Review: German-Jewish Pioneers in Science 1900–1933. By D. Nachmansohn (pages 573–574)

      Andreas Kleinert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198005732

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