Angewandte Chemie International Edition in English

Cover image for Vol. 33 Issue 4

March 3, 1994

Volume 33, Issue 4

Pages 367–484

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 4/1994)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199403651

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      The cover picture shows a balance with 1.5010 g of the enantiomerically pure, chiral ketone whose formula is given on the right-hand side of the picture. This compound was synthesized on a preparative scale by the antibody-catalyzed enantioselective hydrolysis of the enol ether shown on the left-hand side. The monoclonal antibody was raised against a hapten (general structure in the box) which is an analogue of the transition state depicted at the top. Thus, catalytic antibodies (see for example the highlight by C. Leumann last year: Angew. Chem.1993, 105, 1352; Angew. Chem. Int. Ed. Engl.1993, 32, 1291) can be considered as practical tools for preparative chemistry. J.-L. Reymond, J.-L. Reber, and R. A. Lerner give details on upscaling on pp. 475–477.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Correspondences
    5. Communications
    6. Book Reviews
    1. Template Syntheses (pages 375–384)

      Dr. Ralf Hoss and Prof. Dr. Fritz Vögtle

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199403751

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      Template syntheses—old hat? Not so! With a selection of topical examples, this systematic overview shows that the concept covers far more than the synthesis of macrocyclic ligands in the coordination sphere of metal ions [Eq. (a)]. There are ionic and neutral, atomic and molecular, covalently and noncovalently bound, positive and negative, permanent and temporary, internal and external, and concave and convex templates.

    2. Organic and Organometallic Molecular Magnetic Materials—Designer Magnets (pages 385–415)

      Dr. Joel S. Miller and Dr. Arthur J. Epstein

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199403851

      The design of new magnetic materials based on molecular species, which are of interest for a variety of applications, remains an art. To achieve the required spin couplings for bulk ferro- or ferrimagnetic behavior it is crucial to prepare materials with very specific primary, secondary, and tertiary structures. Cooperative magnetic phenomena in the solid state is exhibited by, for example, several organometallic solids, which comprised linear chains of metallocenium donors D and cyanocarbon acceptors A (…D•+ A•− D•+ A•−…).

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Correspondences
    5. Communications
    6. Book Reviews
    1. Catalytic Enantioselective C[BOND]C Coupling—Allyl Transfer and Mukaiyama Aldol Reaction (pages 417–419)

      Dr. Thorsten Bach

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404171

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      To obtain enantiomerically pure products without using stoichiometric quantities of chiral components is now possible for the title reactions [Eq. (a)]. Chiral Lewis acids M′Xn are employed, which enable an excellent facial differentiation. In some cases these catalysts provide enantiomeric excesses greater than 95% and outstanding chemical yields.

    2. Making and Breaking of Si[BOND]E (E = C, Si) Bonds by Oxidative Addition and Reductive Elimination Reactions (pages 419–421)

      Prof. Dr. Ulrich Schubert

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404191

      Important steps in metal-mediated stoichiometric or catalytic reactions of organosilicon compounds are oxidative additions and reductive eliminations. Although the tools to tune the ability of a metal complex fragment to undergo such reactions are, in principle, known—for example, oxidative additions are facilitated by metals which are easily oxidized and by small ancillary ligands—the challenge for the chemist is to make these reactions, particularly for Si[BOND]C and Si[BOND]Si bonds, more predictable.

    3. Conocurvone—Prototype of a New Class of Anti-HIV Active Compounds?** (pages 422–424)

      Prof. Dr. Hartmut Laatsch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404221

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      The trimeric naphthoquinone derivative 1 averts the death of HIV-1-infected human lymphoblastoid cells, simultaneously stops the virus replication, and in cell tests shows an exceptionally high therapeutic index for a virostatic agent. The structure of 1 was elucidated by synthesis. R = CH2CH2CH[DOUBLE BOND]CMe2.

  3. Correspondences

    1. Top of page
    2. Reviews
    3. Highlights
    4. Correspondences
    5. Communications
    6. Book Reviews
    1. Bond-Stretch Isomers: Fact not Fiction (pages 425–427)

      Prof. Dr. Philipp Gütlich, Prof. Dr. Harold A. Goodwin and Prof. Dr. David N. Hendrickson

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404251

      The conversion from the low-spin to the high-spin state in spin-crossover transition metal complexes leads to bond-length isomers, since the distance between the metal center and the coordinating ligand atom necessarily increases by 0.04–0.28Å. The coexistence of two such isomers and the effect of temperature and irradiation on their interconversion has been demonstrated by Mössbauer spectroscopy.

  4. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Correspondences
    5. Communications
    6. Book Reviews
    1. Crystal Structure of a Supramolecular Dimer Formed by π[BOND]π Interactions between Two Interlocked Cyclic Zinc Porphyrin Trimers (pages 429–431)

      Dr. Harry L. Anderson, Alan Bashall, Dr. Kim Henrick, Prof. Mary McPartlin and Dr. Jeremy K. M. Sanders

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404291

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      Dimers of trimers are found in the crystal structure of the pyridine adduct of a zinc porphyrin macrocycle (structure shown on the right). The analogous quinuclidine adduct does not show the interpenetration of two zinc porphyrin trimers that probably results from π[BOND]π interactions (T and stacking arrangements) between the pyrrole and pyridine rings.

    2. Schiff Base Complexes with Five-Coordinate Cobalt as Dioxygen Activating Sites in Zeolites (pages 431–433)

      Dirk E. De Vos, Dr. Frédéric Thibault-Starzyk and Prof. Dr. Peter A. Jacobs

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404311

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      Cages of cubic faujasite FAU and its hexagonal polymorph EMT can house Co2+ complexes of the pentadentate Schiff base smdpt (structure from computer simulations shown on the right). The influence of the framework topology on complexation was examined. In addition, these enclosed complexes can bind dioxygen reversibly as proved by ESR studies. H2smdpt = bis[3-(salicylidenamino)propyl]methylamine.

    3. The Two-Step Self-Assembly of [4]- and [5]Catenanes (pages 433–437)

      Dr. David B. Amabilino, Peter R. Ashton, Anatoli S. Reder, Dr. Neil Spencer and Prof. J. Fraser Stoddart

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404331

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      Advances through very specific techniques for template-directed synthesis and analysis is the name of the game for oligo- and polycatenanes. Under high pressure and with the support of donor–acceptor association phenomena, it was possible to synthesize a [4]-(schematic view shown here) and a [5]catenane. These chains—in the true sense!—are interesting starting units for a series of new polymers. Modern mass spectrometric techniques were essential for their characterization.

    4. Fullerene Chemistry in Three Dimensions: Isolation of Seven Regioisomeric Bisadducts and Chiral Trisadducts of C60 and Di(ethoxycarbonyl)methylene (pages 437–438)

      Dr. Andreas Hirsch, Iris Lamparth and Priv.-Doz. Heinrich R. Karfunkel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404371

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      Remarkably high selectivity marks the reaction of a regioisomeric bisadduct of C60 with defined structure to give the D3-symmetric trisadduct 1. This and other results—for example, the isolation of the seven stable isomers of C62(COOEt)4 (of the eight possible)—were obtained in the first systematic study of the regiochemistry of C60 with both experimental and theoretical methods.

    5. Preparation and C-Alkylation of Peptides with Aminomalonate Building Blocks (pages 439–440)

      Dr. Hans G. Bossler, Dipl.-Chem. Pius Waldmeier and Prof. Dr. Dieter Seebach

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404391

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      The preparation of a whole series of peptides—starting from a single precursor—can be achieved with readily available tripeptides such as 1 (R = H). They contain aminomalonate building blocks which can be alkylated with alkyl halides and Michael acceptors under basic conditions in good to excellent yields. By cleavage of the benzyloxycarbonyl group, peptide derivatives 1, R = alkyl, etc. are obtained, which can then be further modified. Such peptide series are of particular interest, for example, for screenings (“peptide libraries”).

    6. Chiral Dendrimers from Tris(hydroxymethyl)methane Derivatives (pages 440–442)

      Prof. Dr. Dieter Seebach, Dr. Jean-Marc Lapierre, Dr. Konstantinos Skobridis and Dipl.-Chem. Guy Greiveldinger

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404401

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      The first dendrimer with a chiral core and chiral branch units (2) is readily available from triols of the type 1. Attachment of spacer groups or direct etherification of 1 with benzylic bromides lead to first, second, and third generation chiral dendrimers. The molecular weights of the fully characterized dendrimers range between 1000 and 3000 Da. The dendrimer 2, built up from four chiral building blocks, is one out of 4096 possible stereoisomers.

    7. Cyclosporin: A Li- and Ca-Specific Ionophore! (pages 442–444)

      Dr. H. Michael Bürger and Prof. Dr. Dieter Seebach

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404421

      The ionophoric properties of cyclosporin shed new light on its role in immunosuppresion: Cyclosporin transports Li+ and Ca2+ significantly faster than appropriate for their position in the series of alkali metal and alkaline-earth metal ions, respectively. The migration of the picrates of these metals through a CH2Cl2 solution of cyclosporin (which functions as a liquid membrane) has been examined.

    8. Diastereoselective Hydroxyalkylation of Enantiomerically Pure 2-Alkenylsulfoximides (pages 444–446)

      Dr. Michael Reggelin and Dipl.-Chem. Heinz Weinberger

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404441

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      Excellent asymmetric induction stems from the chiral center at sulfur in the new asymmetric C3 building blocks 1 and 2. These compounds have an unusual property useful for C1-substituted chiral allyl transfer agents: the lithiated intermediates are configurationally labile. Subsequent reactions can be carried out stereoconvergently to give diastereomerically and enantiomerically pure products. H2NVal = O-trimethylsilylvalinol.

    9. Novel Molecular Scaffolds: Formation of Helical Secondary Structure in a Family of Oligoanthranilamides (pages 446–448)

      Yoshitomo Hamuro, Dr. Steven J. Geib and Prof. Andrew D. Hamilton

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404461

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      In a simple reaction sequence 2-nitrobenzoyl chloride, methyl anthranilate, and 2,6-bis-(chloroformyl)pyridine are employed to give oligoanthranilamide 1. This compound has a helical structure in solution and in the solid state, and the pitch of the helix can be altered by synthesis of the corresponding pyridine N-oxide derivative. These types of mimics of the peptide framework are of interest for the de novo design of proteins and drugs.

    10. Generation of the Parent Allyl Cation in a Superacid Cryogenic Matrix (pages 448–451)

      Dr. Peter Buzek, Prof. Paul von R. Schleyer, Dr. Hrvoj Vančik, Dr. Zlatko Mihalic and Dr. Jürgen Gauss

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404481

      By using cyclopropyl bromide as precursor, the allyl cation C3Hmath image can be generated at low temperature in an SbF5 matrix and observed by IR spectroscopy; the experimental IR spectrum agrees well with that computed by ab initio methods. Characterization by 13C NMR spectroscopy failed, but the 13C NMR chemical shifts of this and other allyl cations could be predicted accurately for the first time by the GIAO/MP-2 method.

    11. Novel Conjunction of Hetero(macro)cycles and a Pentamolybdodiphosphonate Cage (pages 451–454)

      Mark P. Lowe, Dr. Joyce C. Lockhart, Prof. William Clegg and Kelly A. Fraser

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404511

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      Supramolecular chemistry with polyoxometalates should be possible by linking a crown ether with a molybdophosphonate. The synthesis of the guanidinium salt of [Mo5(ZP)2O21]2− (structure shown on the right, Z = morpholinomethyl or monoaza - [15] crown - 5 - methyl), whose solid-state structure is influenced by hydrogen bonds, points the way to this new class of compounds.

    12. Enantioselective Reactions in a Static Magnetic Field (pages 454–456)

      Dr. Guido Zadel, Dipl.-Chem. Catia Eisenbraun, Dr. Gerd-Joachim Wolff and Prof. Dr. Eberhard Breitmaier

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404541

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      Additions to polar double bonds can proceed with enantiomeric excesses of up to 98% when the reaction is conducted in a static magnetic field. The Grignard alkylation of aldehydes and the reduction of ketones with lithium aluminum hydride were used to demonstrate this novel type of chiral induction. R′ = Me, Et; R = Ph, 2-naphthyl, Et.

    13. A Stannanediyl with a Tin[BOND]Carbon Multiple Bond (pages 456–458)

      Prof. Dr. Hansjörg Grützmacher, Dr. Werner Deck, Dr. Hans Pritzkow and Dipl.-Chem. Michael Sander

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404561

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      A novel ligand coupling reaction on a low-coordinate Sn atom occurs in the reaction of the ketene ylide 2 with the stannanediyl 1 (R = 2,4,6-(CF3)C6H2) almost quantitatively to give 3. The Sn[BOND]C distances in 3 suggest a Sn[BOND]C multiple bond in the central planar CCPSnC framework.

    14. Diastereoselective Synthesis of Amino-Substituted Indolizidines and Quinolizidines by the Intramolecular Hetero-Ene Reaction of Prolinal Imine and 2-Piperidine Carbaldimine (pages 458–461)

      Dr. Sabine Laschat and Dr. Matthias Grehl

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404581

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      The choice of Lewis acid determines the stereochemistry and structure of the products in the cyclization of 1. Whereas with FeCl3 the benzylamino(isopropenyl) compounds 2 are formed preferably, in the presence of TiCl4 the main products are benzylideneamino(isopropyl)-substituted compounds 3.

    15. Structural Principles in Seven-Coordinate Subgroup Compounds: The Complex Anions MoFmath image, WFmath image, and ReOFmath image (pages 461–463)

      Dipl.-Chem. Steffi Giese and Prof. Dr. Konrad Seppelt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404611

      Which coordination polyhedron occurs for compounds with coordination number seven? For d0 subgroup compounds the principle of the highest possible symmetry holds; in other words, capped octahedra result for complexes with seven identical ligands and when the interionic forces can be neglected. This is in sharp contrast to the analogous main group compounds, which form pentagonal bipyramids. When subgroup compounds contain one larger ligand and six smaller ones, pentagonalbipyramidal structures occur.

    16. Novel Trimerization of Phosphaalkynes in the Coordination Sphere of Ruthenium Complexes (pages 463–465)

      Dr. Peter B. Hitchcock, Dr. Cameron Jones and Prof. John F. Nixon

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404631

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      A 2-phosphaallylic center and a fluoro-substituted phosphonium center are present in the novel complex 1, which is formed by a trimerization reaction of t BuC[TRIPLE BOND]P with [CpRu(CH3CN)3][PF6]. Subsequent reaction of 1 with two equivalents of [W(CO)5(thf)] affords 2, the first 2-phosphaallyl complex in which this ligand is coordinated η1 and η3 to two metal centers.

    17. 2H,5H-Benzo[l,2-b:4,5-b′]bisthiete—A Highly Reactive Bisdiene System (pages 465–467)

      Prof. Dr. Herbert Meier and Dipl.-Chem. Axel Mayer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404651

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      The title compound 2 is a rigid molecule with two potential 1,3-diene units. It was synthesized in three steps from the diester 1. The successive opening of the four-membered rings of 2 enables the construction of linear annelated ring systems and band structures; for example, the reaction with dimethyl acetylenedicarboxylate leads to the tricycle 3.

    18. A Difunctional Receptor for the Simultaneous Complexation of Anions and Cations; Recognition of KH2PO4 (pages 467–468)

      Dr. Ir. Dmitry M. Rudkevich, Dr. Ir. Zbigniew Brzozka, Dr. Marcin Palys, Dr. Herman C. Visser, Dr. Willem Verboom and Prof. Dr. Ir. David N. Reinhoudt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404671

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      The Lewis acidic uranyl center and the amide units of receptor 1 bind the anion of the hydrophilic, biologically relevant salt KH2PO4 specifically, and simultaneously the crown ether units bind the cation. The complexation properties of 1 were studied with NMR spectroscopy, mass spectrometry, and cyclic voltammetry. The recognition demonstrated for this simple salt could be of great importance for membrane transport, extraction, and sensor technology.

    19. Expanded Radialenes: A Novel Class of Cross-Conjugated Macrocycles (pages 468–471)

      Armen M. Boldi and Prof. Dr. François Diederich

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404681

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      Large cores composed exclusively of carbon, substituents only on the periphery, and nanometer-scale dimensions—these are the characteristics of the title compounds 1 (n = 1; C40 + 8SiiPr3), 2 (n = 2; C50 + 10SiiPr3), and 3 (n = 3; C60 + 12SiiPr3). The π-electron delocalization in these molecules is limited to the longest linearly conjugated fragment (TIPS = triisopropylsilyl).

    20. Selective Catalysis on Silicon Dioxide with Substrate-Specific Cavities (pages 471–473)

      Dipl.-Chem. Jens Heilmann and Prof. Dr. Wilhelm F. Maier

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404711

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      By building a transition state analogue of the transesterification of ethyl phenylacetate to the hexyl ester into the SiO2 matrix during the sol–gel process (see sketch) and subsequently removing it, a selective and highly active SiO2 catalyst was synthesized. The transesterification with hexanol is approximately as fast as that with octanol, but with phenylethanol the reaction is significantly slower.

    21. Silane Nitrile: Matrix Isolation, Adduct with Hydrogen (pages 473–475)

      Prof. Dr. Günther Maier and Dipl.-Chem. Jörg Glatthaar

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404731

      How do carbon and silicon chemistry differ? For example, the cyanide⇌isocyanide equilibrium is completely reversed in the sila series. According to calculations silane nitrile (2) is higher in energy than its isomer 1, which has been known for much longer. The matrix isolation of 2 has now been achieved; 2 is the first silicon compound of the nitrile type.

      • equation image
    22. Enantioselective, Multigram-Scale Synthesis with a Catalytic Antibody (pages 475–477)

      Dr. Jean-Louis Reymond, Dr. Jean-Louis Reber and Prof. Dr. Richard A. Lerner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404751

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      The enantioselective conversion of the achiral enol ether 1 into the chiral ketone 2 was carried out on a multigram-scale with a monoclonal antibody (Ab). This procedure requires only conventional laboratory equipment.

  5. Book Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Correspondences
    5. Communications
    6. Book Reviews
    1. Book Review: The Organic Chemistry of β-Lactams. Edited by G. I. Georg (page 480)

      Jens Nieschalk and Ernst Schaumann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199404801