Angewandte Chemie International Edition in English

Cover image for Vol. 36 Issue 9

May 16, 1997

Volume 36, Issue 9

Pages 899–1017

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 9/1997)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199708971

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      The cover picture shows a model of the binding of a protonated cyclopropane in a cation-binding site of an antibody. The larger circle gives an enlarged view of the actual binding of the organic intermediate. The aromatic and carboxylate groups are yellow, the organic intermediate silver, and the carbon atoms of the protonated cyclopropane red. The image was created with the programs Persistence of Vision and RasMol as well as proprietary software by Dr. Nicholas C. DeMello. More on the stabilization of cyclopropane intermediates is reported by J. K. Lee and K. N. Houk on pages 1003 ff.

  1. Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Corrigenda
    5. Communications
    6. Book Reviews
    1. Superstructures of Functional Colloids: Chemistry on the Nanometer Scale (pages 910–928)

      Prof. Dr. Markus Antonietti and Dr. Christine Göltner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709101

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      Suitable handling of a delicate balance of van der Waals, hydrogen bonding, and electrostatic interaction allows the preorganization of matter on the nanometer scale and hence the controlled synthesis of functional colloids. This approach opens access to materials with unique properties or combinations of properties, and sometimes of great beauty. The picture shows calcium carbonate “chrysanthemum particles” with a diameter of about 210 nm, which are grown in the presence of structure-regulating functional polymers.

    2. A New Synthetic Strategy towards Molecules with Mechanical Bonds: Nonionic Template Synthesis of Amide-Linked Catenanes and Rotaxanes (pages 930–944)

      Dipl.-Chem. Ralf Jäger and Prof. Dr. Fritz Vögtle

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709301

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      Prepared from simple diacid dichlorides and diamines, catenanes and rotaxanes, once thought exotic, can be synthesized in up to 40% yield, sometimes in one-step syntheses. The process of threading a stringlike molecule through a neutral template discovered in 1992 is supported by hydrogen bonding and π–π interactions. The quantities of these mechanically bonded molecules are sufficient for further preparative conversions; even complicated topologies like a “molecular pretzel” [Equation (a)] have already been prepared.

  2. Highlights

    1. Top of page
    2. Reviews
    3. Highlights
    4. Corrigenda
    5. Communications
    6. Book Reviews
    1. Amorphous Plastics Pave the Way to Widespread Holographic Applications (pages 945–948)

      Dr. Klaus Meerholz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709451

      Noncrystalline organic photorefractive materials appear to be on the verge of widespread applications such as holographic storage and real-time holographic processing. The performance levels of these materials, which are attracting increasing interest, are close to, and in some respects even beyond those of their long-known inorganic counterparts.

    2. Non-Biaryl Atropisomers: New Classes of Chiral Reagents, Auxiliaries, and Ligands? (pages 949–951)

      Dr. Jonathan Clayden

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709491

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      Commonly observed, but rarely exploited, is the restricted rotation about C[BOND]C single bonds inherent in certain non-biaryl compounds. Recent examples of stereoselective reactions directed by atropisomeric amides (such as that shown below) point the way to a future for these compounds as tools for asymmetric synthesis.

  3. Corrigenda

    1. Top of page
    2. Reviews
    3. Highlights
    4. Corrigenda
    5. Communications
    6. Book Reviews
    1. You have free access to this content
      Corrigendum (page 951)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709511

  4. Communications

    1. Top of page
    2. Reviews
    3. Highlights
    4. Corrigenda
    5. Communications
    6. Book Reviews
    1. Towards Radiation-Sensitive Quasi-Biological Display (pages 954–955)

      Franciscus M. H. de Groot, Prof. Giovanni Gottarelli, Dr. Stefano Masiero, Dr. Gloria Proni, Prof. Gian Piero Spada and Dr. Nicoletta Dolci

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709541

      The pitch of the columnar cholesteric mesophase formed by the dinucleoside phosphate d(GpG) and water becomes shorter after exposure to γ radiation. This effect can be measured directly with an optical microscope from the distance between the fingerprint lines. The inverse pitch is linearly correlated to the dose absorbed between 0 and 20 kGy.

    2. Monitoring In Situ Growth and Dissolution of Molecular Crystals: Towards Determination of the Growth Units (pages 955–959)

      Dr. David Gidalevitz, Prof. Robert Feidenhans'l, Dr. Sophie Matlis, Dr. Detlef-M. Smilgies, Dr. Morten J. Christensen and Prof. Leslie Leiserowitz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709551

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      Cyclic, hydrogen-bonded dimers are shown to be the building blocks of α-glycine and of β-alanine crystals by atomic force microscopy and surface X-ray diffraction experiments on their growth and dissolution (one such unit of β-alanine is shown on the right). Both processes take place in steps of hydrogen-bonded bilayers.

    3. Surface X-ray Scattering Study of Stereospecific Adsorption of Additives onto the Surface of a Molecular Crystal Grown from Solution (pages 959–962)

      Dr. David Gidalevitz, Prof. Robert Feidenhans'l and Prof. Leslie Leiserowitz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709591

      An ordered layer of (S)-methionine is attached to the (010) face of α-glycine when the crystals are brought into contact with a saturated solution of glycine containing (S)-methionine as additive. The direct evidence was obtained by grazing incidence X-ray scattering experiments, which also indicated different behavior for the (010) and (010) faces. The concentration of the surface-bound methionine molecules was determined to be 4:1.

    4. Design of Antisense (Complementary) Peptides as Selective Inhibitors of Cytokine Interleukin-1 (pages 962–967)

      Dr. Joseph W. Davids, Ali El-Bakri, Jonathan Heal, Dr. Gary Christie, Dr. Gareth W Roberts, Dr. John G. Raynes and Dr. Andrew D. Miller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709621

      The ability of sense peptides (coded for by sense DNA) and corresponding antisense peptides (coded for by corresponding antisense DNA) to interact specifically was used to design antisense peptide inhibitors of interleukin-1 isoforms IL-1β and IL-1α. These inhibitors appear to act as “mini receptors”, binding to both isoforms and thereby sterically blocking the normal interaction between interleukin-1 and its receptors.

    5. A Synthetic Transmembrane Channel Active in Lipid Bilayers (pages 967–969)

      Jean-Christophe Meillon and Dr. Normand Voyer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709671

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      An artificial ion channel active in planar lipid membranes: the 21 amino acid peptide 1 mimics the K+ ion transport ability of natural ion-channel proteins. Peptide 1 assumes an α-helical conformation in the membrane, and its crown ether units are aligned to form a polar passageway for ions across the lipid bilayer.

    6. Crystal Engineering of Melamine–Imide Complexes; Tuning the Stoichiometry by Steric Hindrance of the Imide Carbonyl Groups (pages 969–971)

      Ronald F. M. Lange, Felix H. Beijer, Dr. Rint P. Sijbesma, Dr. Rob W. W. Hooft, Dr. Huub Kooijman, Dr. Anthony L. Spek, Prof. Jan Kroon and Prof. Dr. E. W. Meijer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709691

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      A defined melamine–imide ratio in cocrystals can be selected by changing the steric hindrance around the hydrogen-bond acceptor sites of the imides. Crystalline 1:1, 1:2, and 1:3 complexes of melamine may thus be obtained with succinimide, glutarimide, and 1-N-propylthymine (see picture), respectively.

    7. Supramolecular Isomerism in Coordination Polymers: Conformational Freedom of Ligands in [Co(NO3)2(1,2-bis(4-pyridyl)ethane)1.5]n (pages 972–973)

      Tracy L. Hennigar, Donald C. MacQuarrie, Dr. Pierre Losier, Prof. Robin D. Rogers and Prof. Dr. Michael J. Zaworotko

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709721

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      Bilayers or open-framework ladder structure? Which supramolecular isomer is formed from Co(NO3)2 and the nonrigid spacer 1,2-bis(2-pyridyl)ethane depends on the crystallization conditions. The open-framework coordination polymer contains large, square cavities of 10 × 10 Å. A section of the bilayer motif is shown on the right.

    8. Synthesis of Boryl Metal Complexes with Additional Agostic Stabilization by Hydroboration of Fischer Carbyne Complexes (pages 974–976)

      Priv.-Doz. Dr. Hubert Wadepohl, Dipl.-Chem. Ulrich Arnold and Dr. Hans Pritzkow

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709741

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      At first glance, the products 1 obtained from the hydroboration of some Fischer carbyne complexes are rather unexpected. They are of interest, not only because of the agostic interaction, but also because X-ray crystallographic and spectroscopic findings point to considerable multiple-bond character of the M[BOND]B bonds.

    9. Mechanistic Insights into the Very Efficient [ReO3OSiR3]-Catalyzed Isomerization of Allyl Alcohols (pages 976–978)

      Stéphane Bellemin-Laponnaz, Dr. Hervé Gisie, Dr. Jean Pierre Le Ny and Prof. John A. Osborn

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709761

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      The catalytic isomerization of allyl alcohols by a 1,3-OH shift can be carried out very rapidly in the presence of [ReO3OSiR3] catalysts at 25°C or below [Eq. (a)]. Kinetic studies suggest that the rearrangement takes place via a cyclic transition state involving a Re = O group. R = Me, Ph.

    10. [H3N(CH2)2NH3]math image[Sn4P3O12]: An Open-Framework Tin(II) Phosphate (pages 978–980)

      Dr. Srinivasan Natarajan, Dr. Martin P. Attfield and Prof. Anthony K. Cheetham

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709781

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      Colorless en-SnPO-1, the title compound, crystallizes in the space group Pnaa and forms a network of alternating pyramidal SnO3 and tetrahedral PO4 moieties in which all the vertices are shared. The structure-directing agent, diprotonated ethylenediamine, is located in an eight-ring channel system. The SnII lone pairs protrude into a second channel system comprising squashed twenty-rings (see picture).

    11. A Highly Stereoselective Synthesis of β-Trifluoromethylated Homoallylic Alchols in Water (pages 980–982)

      Dr. Teck-Peng Loh and Xu-Ran Li

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709801

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      A tin-mediated, indium trichloride promoted allylation reaction provided β-trifluoromethylated homoallylic alcohols, the building blocks of biologically active substances, in high yields and excellent stereoselectivity (see below; R = H, Cy, Ar, COOH). Since the syntheses can be carried out in water, the reactive OH groups do not need to be protected, and even compounds that are insoluble in organic solvents can be used.

    12. (CuI)3Cu2TeS3: Layers of Cu2TeS3 in Copper(I) Iodide (pages 982–984)

      Dr. Arno Pfitzner and Dr. Stefan Zimmerer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709821

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      A description as a composite of CU2TeS3 and CuI is possible for (CuI)3Cu2TeS3, the first representative of a series of compounds formed by complex chalcogenometalate ions and copper(I) halides. The (TeS3)2− groups are oriented in parallel columns between layers of iodide ions (section of the crystal structure depicted on the right).

    13. Intermediates in the Intermolecular, Asymmetric Heck Arylation of Dihydrofurans (pages 984–987)

      Dr. King Kuok (Mimi) Hii, Dr. Timothy D. W. Claridge and Dr. John M. Brown

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709841

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      Double isomerization results in a Pd-alkyl compound with unexpected structure, which is stable until −40°, from the reaction of the Pd complex shown on the right with 2,3-dihydrofuran. The course of the asymmetric Heck reaction was followed by NMR spectroscopy.

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    14. Zirconocen–Benzyme-Mediated Intramolecular Coupling of Bis(alkynyl)phosphane: A Way to Mono- and Tricyclic 1,2-Dihydrophosphetes (pages 987–989)

      Laurence Dupuis, Dr. Nadine Pirio, Prof. Philippe Meunier, Dr. Alain Igau, Bruno Donnadieu and Dr. Jean-Pierre Majoral

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709871

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      The tricyclic zirconium complex 2 is formed when transient zirconocene–benzyne is allowed to react with bis(alkynyl)phosphane 1. Further reactions with 2 lead to mono- and tricyclic 1,2-dihydrophosphetes.

    15. IR Spectroscopic Evidence for the Absence of Structural Hydroxyl Groups in Cloverite (pages 989–991)

      Dr. Frédéric Thibault-Starzyk, André Janin and Dr. Jean-Claude Lavalley

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709891

      Little or no Brønsted acidity is exhibited by the large-pore molecular sieve cloverite according to quantitative IR spectroscopic investigations. Only 3.5% of the expected 192 hydroxyl groups per unit cell suggested by the X-ray structure are detected.

    16. Hydrothermal Synthesis of Microporous Transition Metal Squarates: Preparation and Structure of [CO33-OH)2(C4O4)2]·3H2O (pages 991–992)

      Siegfried O. H. Gutschke, Dr. Michel Molinier, Dr. Annie K. Powell and Dr. Paul T. Wood

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709911

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      A cobalt hydroxide backbone with a structure reminiscent of that found in cobalt(II) hydroxide forms the basis of the framework of the title compound. The squarate ligands of this coordination solid link the metal hydroxide strips together and form the walls of channels with a diameter of approximately 7 Å.

    17. Small Gold Clusters with Carborane Ligands: Synthesis and Structural Characterization of the Novel Compound [Au4{(PPh2)2C2B9H10}2(AsPh3)2] (pages 993–995)

      Dr. Olga Crespo, Dr. M. Concepión Gimeno, Prof. Dr. Peter G. Jones, Prof. Dr. Antonio Laguna and Dr. M. Dolores Villacampa

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709931

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      Depending on the stoichiometric ratio of the reactants, the reaction of [AuCl(AsPh3)] with (PPh2)2C2B10H10 in ethanol at reflux gives two very different compounds containing partially degraded carborane moieties: the four-coordinate complex [Au{(PPh2)2C2B9H10}{(PPh2)2C2B10H10}] or the novel gold cluster [Au4{(PPh2)2C2B9H10}2(AsPh3)2] (depicted on the right).

    18. Asymmetric Synthesis of α-Methyl α-Amino Acids by Diastereoselective Alkylation of Optically Active 6-Isopropyl-3-methyl-2,3—dihydro-6H-1,4-oxazin-2-ones (pages 995–997)

      Dr. Rafael Chinchilla, Prof. Dr. Larry R. Falvello, Nuria Galindo and Prof. Dr. Carmen Nájera

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709951

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      At room temperature already highly diastereoselective alkylation of the new, cyclic, chiral alanine ester derivatives (6R)-1 can been achieved with either K2CO3 as base under solid–liquid phase-transfer catalysis or Pd catalysis unter neutral conditions. The products (3S,6R)-2 can be easily hydrolyzed to form (S)-α-methyl α-amino acids.

    19. Dioxygen Binding at Ambient Temperature: Formation of a Novel Peroxodicopper(II) Complex with an Azole Macrocyclic Ligand (pages 998–1000)

      Dr. Johan E. Bol, Dr. Willem L. Driessen, Dr. Raymond Y. N. Ho, Bas Maase, Prof. Dr. Lawrence Que Jr. and Prof. Dr. Jan Reedijk

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199709981

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      The protective pocket of hemocyanin is mimicked by the novel macrocyclic ligand MEPY22PZ (see schematic drawing on the right), which was used to make a Cu2[BOND]O2 adduct. Proper design of a ligand with azole donors connected by ethylene spacers illustrates how metal–O2 adducts can be stabilized at ambient temperatures and in protic solvents. The purple trans-μ-1,2-CuII-O2-CuII species was obtained by oxygenation of the parent CuI compound and by addition of H2O2 and base to the dinuclear CuII complex.

    20. Soluble Molecular Titanosilicates (pages 1001–1003)

      Dr. Andreas Voigt, Dr. Ramaswamy Murugavel, Dr. Mavis L. Montero, Dipl.-Chem. Helge Wessel, Dr. Feng-Quan Liu, Prof. Dr. Herbert W. Roesky, Dr. Isabel Usón, Thomas Albers and Dr. Emilio Parisini

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199710011

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      Titanosilicates with structural characteristics similar to those of many Ti-containing zeolites were synthesized from the reactions of (arylamino)silanetriol [RSi(OH)3] with organometallic titanium precursors [Cp*TiCl3], TiCl4·2THF, and [Cp*TiMe(μ-O)]3. The product of the reaction with [Cp*TiCl3], 1, is a soluble molecular silicate in which formal TiO2 fragments are trapped inside. Cp* = C5Me5; R = (2,6-iPr2C6H3)NSiMe3.

    21. Cation-Cyclization Selectivity: Variable Structures of Protonated Cyclopropanes and Selectivity Control by Catalytic Antibodies (pages 1003–1005)

      Dr. Jeehiun K. Lee and Prof. Kendall N. Houk

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199710031

      A nonclassical, protonated cyclopropane is the intermediate formed in an antibodycatalyzed cyclization reaction. The selectivity in favor of the cyclopropane product is increased upon binding of the catalytic antibody, which amplifies the inherent preference for one reaction pathway.

    22. Noncovalent Synthesis of Nanostructures: Combining Coordination Chemistry and Hydrogen Bonding (pages 1006–1008)

      Drs. Wilhelm T. S. Huck, Dr. Ron Hulst, Dr. Peter Timmerman, Dr. Ir. Frank C. J. M. van Veggel and Prof. Dr. Ir. David N. Reinhoudt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199710061

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      Rosettes that are held together by hydrogen bonds (see sketch on the right) were synthesized from metallodendrimers constructed by coordination chemistry. Two orthogonal, noncovalent interactions (metal–ligand and hydrogen bonding) were employed to build these nanosized dendrimers (M ≈ 7–28 kDa).

    23. Novel Clusters of Transition Metals and Main Group Oxides in the Alkylamine/Oxovanadium/Borate System (pages 1008–1010)

      Job T. Rijssenbeek, David J. Rose, Dr. Robert C. Haushalter and Prof. Jon Zubieta

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199710081

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      Unprecedented structural and compositional features are exhibited by these large vanadium borate clusters (for example 1, see picture on the right). Facile solubilization and crystallization of transition metal oxides by these large, multidentate polyborate ligands portends a rich and diverse chemistry for transition element/polyborate clusters. en = ethylenediamine.

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    24. Super Oil-Repellent Surfaces (pages 1011–1012)

      Dr. Kaoru Tsujii, Takamasa Yamamoto, Dr. Tomohiro Onda and Satoshi Shibuichi

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199710111

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      Without sticking to the surface rapeseed oil droplets roll around on a surface prepared in two steps: An aluminum plate is first anodically oxidized and then treated with fluorinated monoalkylphosphates. The contact angles for some polar oils on such surfaces are greater than 150°.

    25. 61 Helices from Tetrahedral Ribbons math image[BP2Omath image]: Isostructural Borophosphates MIMII(H2O)2[BP2O8] · H2O (MI = Na, K; MII = Mg, Mn, Fe, Co, Ni, Zn) and Their Dehydration to Microporous Phases MIMII(H2O)[BP2O8] (pages 1013–1014)

      Prof. Dr. Rüdiger Kniep, Dipl.-Ing. Horst Günter Will, Dipl.-Ing. Insan Boy and Dr. Caroline Röhr

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.199710131

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      Together with the MI ions, the tetrahedral ribbons of the title compounds form double helices, the central channels of which are filled with water helices (see picture). Coordination octahedra MIIO4(H2O)2 link the spiral ribbons, which run parallel to one another. Partial dehydration of the title compounds leads to microporous phases with channeled structure and is reversible in the sense of a topochemical reaction.

  5. Book Reviews

    1. Top of page
    2. Reviews
    3. Highlights
    4. Corrigenda
    5. Communications
    6. Book Reviews