Angewandte Chemie International Edition

Cover image for Vol. 45 Issue 11

March 6, 2006

Volume 45, Issue 11

Pages 1661–1819

  1. Cover Picture

    1. Top of page
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    4. Corrigendum
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    6. Book Review
    7. Highlight
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    1. Cover Picture: Syntheses, Structures, and Reactivity of Radial Oligocyclopentadienyl Metal Complexes: Penta(ferrocenyl)cyclopentadienyl and Congeners (Angew. Chem. Int. Ed. 11/2006) (page 1661)

      Yong Yu, Andrew D. Bond, Philip W. Leonard, K. Peter C. Vollhardt and Glenn D. Whitener

      Article first published online: 1 MAR 2006 | DOI: 10.1002/anie.200690036

      True artistry is not limited to the fine arts. Penta(ferrocenyl)cyclopentadienyl complexes like that shown display intriguing structures and reactivity. In their Communication on page 1794 ff., K. P. C. Vollhardt et al. describe penta(ferrocenyl)cyclopentadienyl compounds that have ramifications for materials science, catalysis, and fundamental chemistry. (Background for the cover illustration is the painting “Untitled” by the French artist Marie Sat; graphics prepared by P. W. Leonard.)

  2. Graphical Abstract

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  3. Corrigendum

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      The [Ga2(C5Me5)]+ Ion: Bipyramidal Double-Cone Structure and Weakly Coordinated, Monovalent Ga+ (page 1674)

      Beatrice Buchin, Christian Gemel, Thomas Cadenbach, Rochus Schmid and Roland A. Fischer

      Article first published online: 1 MAR 2006 | DOI: 10.1002/anie.200690038

      This article corrects:

      The [Ga2(C5Me5)]+ Ion: Bipyramidal Double-Cone Structure and Weakly Coordinated, Monovalent Ga+1

      Vol. 45, Issue 7, 1074–1076, Article first published online: 15 DEC 2005

  4. News

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  5. Book Review

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  6. Highlight

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    1. Metal Coordination To Assist Molecular Gelation (pages 1680–1682)

      Frédéric Fages

      Article first published online: 1 MAR 2006 | DOI: 10.1002/anie.200503704

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      Gelling together: Molecular gels are a class of nanoscale materials based on the self-assembly of low-molecular-weight compounds. The manipulation of metal–ligand interactions offers novel opportunities to fabricate highly processable and stimuli-responsive metallogels that capitalize on the rich properties of the metal complexes (see picture).

    2. A Catalytic Approach for the Functionalization of C(sp3)[BOND]H Bonds (pages 1683–1684)

      Mamoru Tobisu and Naoto Chatani

      Article first published online: 21 FEB 2006 | DOI: 10.1002/anie.200503866

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      Access allowed: A Lewis acid catalyzed 1,5-hydride shift is the key step in the direct functionalization of sterically congested C(sp3)[BOND]H bonds. This new method complements the existing transition-metal-mediated reactions that are limited to the functionalization of more accessible C[BOND]H bonds.

  7. Review

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    1. Persulfurated Aromatic Compounds (pages 1686–1712)

      Marc Gingras, Jean-Manuel Raimundo and Yoann M. Chabre

      Article first published online: 1 MAR 2006 | DOI: 10.1002/anie.200500032

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      Underexploited despite their mild and high-yielding syntheses, persulfurated arenes have been known for about 50 years. The Review describes the structure and properties of the title compounds and derived materials such as supramolecular assemblies, redox sensors, ion-selective membranes, clathrates, organic conductors, liquid crystals, coordination polymers, and bioinorganic systems.

  8. Communication

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    1. Understanding the Failure of Direct C[BOND]C Coupling in the Zeolite-Catalyzed Methanol-to-Olefin Process (pages 1714–1719)

      David Lesthaeghe, Veronique Van Speybroeck, Guy B. Marin and Michel Waroquier

      Article first published online: 14 FEB 2006 | DOI: 10.1002/anie.200503824

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      You are the weakest link, goodbye! Many individual steps of the direct mechanisms in the methanol-to-olefin process are tied together in an integrated scheme, allowing a simple identification of the weakest links. Calculations show that a combined pathway from methanol directly to ethylene does not exist and no C[BOND]C bond can be formed directly.

    2. Rational Design and First Principles Studies Toward the Discovery of a Small and Versatile Proton Sponge (pages 1719–1721)

      Ernesto Estrada and Yamil Simón-Manso

      Article first published online: 10 FEB 2006 | DOI: 10.1002/anie.200503254

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      Basic principles: The use of simple topological principles permits the design of small molecules with very high proton affinities. According to DFT calculations, 3,6,7,8-tetraazatricyclo[3.1.1.12,4]octane and its analogues behave as superbases, and show important structural deviations from known proton sponges. Their electrostatic potential maps show a characteristic very compact region at the protonation site (blue regions in the picture).

    3. A Structurally Diverse Library of Polycyclic Lactams Resulting from Systematic Placement of Proximal Functional Groups (pages 1722–1726)

      Judith M. Mitchell and Jared T. Shaw

      Article first published online: 15 FEB 2006 | DOI: 10.1002/anie.200503341

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      A short, linear sequence for the synthesis of complex small polycyclic lactams (see picture) is presented. The sequence, which is applied to the synthesis of a library of 529 compounds, is based on a catalytic, enantioselective cycloaddition between an oxazole and an aldehyde, so that the resultant compounds are enantiomerically pure and readily prepared in either stereochemical series.

    4. Selective Immobilization of Proteins onto Solid Supports through Split-Intein-Mediated Protein Trans-Splicing (pages 1726–1729)

      Youngeun Kwon, Matthew A. Coleman and Julio A. Camarero

      Article first published online: 9 FEB 2006 | DOI: 10.1002/anie.200503475

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      Without a trace: The immobilization of biologically active proteins onto a solid support through split-intein-mediated protein trans-splicing reactions requires only very dilute samples. Not only is this process traceless but it does not require purification of the protein, thereby making possible the direct immobilization of proteins from complex mixtures such as cell lysates.

    5. Dysprosium Triangles Showing Single-Molecule Magnet Behavior of Thermally Excited Spin States (pages 1729–1733)

      Jinkui Tang, Ian Hewitt, N. T. Madhu, Guillaume Chastanet, Wolfgang Wernsdorfer, Christopher E. Anson, Cristiano Benelli, Roberta Sessoli and Annie K. Powell

      Article first published online: 23 FEB 2006 | DOI: 10.1002/anie.200503564

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      Roll the Dy's: Two aggregates made up of dysprosium triangles (one example is shown) display a vanishing susceptibility at low temperature, unprecedented in systems comprising an odd number of unpaired electrons. Despite having a near non-magnetic ground state, behavior typical of a single-molecule magnet is observed for the thermally populated excited state.

    6. Mixed Diketonate Thiolate Copper(I) Precursors for Materials Synthesis: Control of Cu2S-Forming Thermolysis Pathways by Manipulating Lewis Acid and Base Cluster Building Blocks (pages 1733–1736)

      Sven Schneider, John A. S. Roberts, Michael R. Salata and Tobin J. Marks

      Article first published online: 7 FEB 2006 | DOI: 10.1002/anie.200503691

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      Scission precision: The combination of Lewis acidic and Lewis basic building blocks in copper(I) thiolate clusters enables control of the thermal decomposition pathway in the design of new molecular precursors for Cu2S formation. After C[BOND]S bond scission, large clusters with cuprous sulfide cores are isolated as intermediates and are structurally characterized (see scheme; hfa=hexafluoroacetylacetonate).

    7. Temperature-Sensitive Core–Shell Microgel Particles with Dense Shell (pages 1737–1741)

      Ingo Berndt, Jan Skov Pedersen and Walter Richtering

      Article first published online: 10 FEB 2006 | DOI: 10.1002/anie.200503888

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      Cores and effect: Using different temperature-sensitive polymers a core–shell microgel is prepared, which at intermediate temperatures has a shell with a higher segment density Φ than the core (see radial density profiles: core (red), shell (blue)). More detailed information is obtained from small-angle neutron scattering. A new form-factor model describes the experimental scattering curves at different temperatures.

    8. Synthesis and Optical Resolution of a Double Helicate Consisting of ortho-Linked Hexaphenol Strands Bridged by Spiroborates (pages 1741–1744)

      Hiroshi Katagiri, Toyoharu Miyagawa, Yoshio Furusho and Eiji Yashima

      Article first published online: 23 FEB 2006 | DOI: 10.1002/anie.200504326

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      Double Twist: The first spiroborate-based helicate was synthesized and shown to be stable in the solid state as well as in solution. The double-stranded structure (see picture) was characterized by 1H NMR spectroscopy, ESI MS, and X-ray crystallographic studies. The racemic helicates were resolved by the formation of a diastereomeric, optically active ammonium salt.

    9. Efficient Gold-Catalyzed Hydroamination of 1,3-Dienes (pages 1744–1747)

      Chad Brouwer and Chuan He

      Article first published online: 2 FEB 2006 | DOI: 10.1002/anie.200504495

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      The Midas touch: 1,3-Dienes undergo hydroamination with carbamates and sulfonamides in the presence of Ph3PAuOTf catalyst under mild conditions (see scheme). The carbobenzyloxy (Cbz) group is readily removed from the product, and the reaction is thus an efficient method to prepare allylic amines.

    10. Gold(I)-Catalyzed Intramolecular Hydroamination of Alkenyl Carbamates (pages 1747–1749)

      Xiaoqing Han and Ross A. Widenhoefer

      Article first published online: 14 FEB 2006 | DOI: 10.1002/anie.200600052

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      Gold for rings: Reaction of alkenyl carbamates such as 1 in the presence of [Au{P(tBu)2(o-biphenyl)}]Cl and AgOTf led to nitrogen heterocycles (e.g. 2). This AuI-catalyzed intramolecular hydroamination tolerates a range of labile carbamates and substitution patterns and can be applied to the synthesis of bicyclic carbamates and protected piperidines. Cbz=benzyloxycarbonyl.

    11. The Solution to a Deep Stereochemical Conundrum: Studies toward the Tetrahydroisoquinoline Alkaloids (pages 1749–1754)

      Collin Chan, Shengping Zheng, Bishan Zhou, Jinsong Guo, Richard M. Heid, Benjamin J. D. Wright and Samuel J. Danishefsky

      Article first published online: 22 FEB 2006 | DOI: 10.1002/anie.200503982

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      Facile construction of subunits 1 and 2 allowed the rapid assembly of the pentacyclic ring system 3 of the cytotoxic tetrahydroisoquinoline alkaloids. A surprising participation reaction was discovered, which necessitated revision of the stereochemical assignments of key intermediates en route to 3.

    12. Stereospecific Formal Total Synthesis of Ecteinascidin 743 (pages 1754–1759)

      Shengping Zheng, Collin Chan, Takeshi Furuuchi, Benjamin J. D. Wright, Bishan Zhou, Jinsong Guo and Samuel J. Danishefsky

      Article first published online: 22 FEB 2006 | DOI: 10.1002/anie.200503983

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      A new strategy was designed for the construction of the pentacyclic ring system of ecteinascidin 743. Key features include highly concise routes to the enantiopure, configurationally matched subunit 1, a novel vinylogous Pictet–Spengler cyclization to 2, and a stereospecific epoxidation and regioselective reduction sequence of the C3[BOND]C4 enamide to secure 3.

    13. Construction of Molecular Logic Gates with a DNA-Cleaving Deoxyribozyme (pages 1759–1762)

      Xi Chen, Yifei Wang, Qiang Liu, Zhizhou Zhang, Chunhai Fan and Lin He

      Article first published online: 10 FEB 2006 | DOI: 10.1002/anie.200502511

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      A logical conclusion: DNA logic gates constructed by using a Cu2+-dependent DNA-cleaving deoxyribozyme are as efficient as the relatively unstable ribonucleotide-containing systems. The inputs (effectors), gates (deoxyribozymes), and outputs (substrates) are represented by chemically robust DNA oligonucleotides, which perform logic operations including “YES”, “NOT”, and “AND(A,NOT(B),NOT(C))” (see picture).

    14. Shaping Amorphous Calcium Carbonate Films into 2D Model Substrates for Bone Cell Culture (pages 1762–1767)

      Daniela C. Popescu, Ellen N. M. van Leeuwen, Nicholas A. A. Rossi, Simon J. Holder, John A. Jansen and Nico A. J. M. Sommerdijk

      Article first published online: 13 FEB 2006 | DOI: 10.1002/anie.200502602

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      Boning up on patterning: Patterned calcium carbonate films with dimensions of 200–400 μm were obtained using the photolithographic properties of a polysilane-based ABA block copolymer, PHEMA-PMPS-PHEMA. These patterns may serve as a 2D model system for CaCO3 biomaterials in which both the CaCO3 resorption by osteoclasts and the calcium phosphate deposition by osteoblasts can be monitored using optical microscopy.

    15. Catalytic Decomposition of Simulants for Chemical Warfare V Agents: Highly Efficient Catalysis of the Methanolysis of Phosphonothioate Esters (pages 1767–1770)

      Stephanie A. Melnychuk, Alexei A. Neverov and R. Stan Brown

      Article first published online: 23 FEB 2006 | DOI: 10.1002/anie.200503182

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      As good as the original: Extremely effective methanolysis of phosphonothioates using metal-containing systems (e.g., 1) was achieved. The catalytic methanolysis of a SCH2CH2NEt2 derivative, an analogue of the organophosphorus chemical warfare material VX, was predicted, and the catalyzed methanolysis of S-(3,5-dichlorophenyl) O-ethyl methylphosphonothioate was shown to involve a concerted displacement of the aryl thioate (transition state 2).

    16. UCST Wetting Transitions of Polyzwitterionic Brushes Driven by Self-Association (pages 1770–1774)

      Omar Azzaroni, Andrew A. Brown and Wilhelm T. S. Huck

      Article first published online: 10 FEB 2006 | DOI: 10.1002/anie.200503264

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      A sweeping success: The surface-initiated, atom-transfer radical polymerization of [2-(methacryloyloxy)ethyl]dimethyl(3-sulfopropyl)ammonium hydroxide (MEDSAH) on silicon and gold surfaces leads to homogeneous and patterned brushes of poly-MEDSAH. The association state of the zwitterionic side-groups is determined (see picture; wettability of thin (left) and thick (right) brushes).

    17. Towards the Determination of the Absolute Configuration of Complex Molecular Systems: Matrix Isolation Vibrational Circular Dichroism Study of (R)-2-Amino-1-propanol (pages 1775–1777)

      György Tarczay, Gábor Magyarfalvi and Elemér Vass

      Article first published online: 14 FEB 2006 | DOI: 10.1002/anie.200503319

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      Molecular freeze-frame: (R)-2-Amino-1-propanol was used as an example to show that matrix isolation vibrational circular dichroism spectroscopy is a useful method for the determination of the absolute configuration of molecules with multiple conformers that are capable of strong intermolecular interactions, especially hydrogen bonds.

    18. Large-Scale Synthesis of H-Antigen Oligosaccharides by Expressing Helicobacter pylori α1,2-Fucosyltransferase in Metabolically Engineered Escherichia coli Cells (pages 1778–1780)

      Sophie Drouillard, Hugues Driguez and Eric Samain

      Article first published online: 14 FEB 2006 | DOI: 10.1002/anie.200503427

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      Sugar production: A microbiological method has been developed for the production of fucosyl α1,2-linked carbohydrates from lactose. The syntheses of 2′-fucosyllactose and lacto-N-neofucopentaose-1 (see structure), which contain the H-2 antigen (Fucα-2Galβ-4R), were achieved by cultivating Escherichia coli strains that overexpressed the appropriate heterologous genes.

    19. A Striking Periodicity of the cis/trans Isomerization of Proline Imide Bonds in Cyclic Disulfide-Bridged Peptides (pages 1780–1783)

      Tiesheng Shi, Stephen M. Spain and Dallas L. Rabenstein

      Article first published online: 10 FEB 2006 | DOI: 10.1002/anie.200503470

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      cispersists: The population of the cis conformation of the Cys–Pro imide bond of the cyclic disulfide form of peptides of the sequence Ac-Cys-Pro-(Xaa)m-Cys-NH2 (Xaa=Phe, Ala) ranges from 9.3 to 76.9 % and shows a striking periodic dependence on the number of residues in the peptide.

    20. Soluble and Liquid-Crystalline Ovalenes (pages 1783–1786)

      Salima Saïdi-Besbes, Éric Grelet and Harald Bock

      Article first published online: 9 FEB 2006 | DOI: 10.1002/anie.200503601

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      The extremely persistent self-assembly of ovalene tetraesters (see picture) into liquid-crystalline columns from below room temperature to over 375 °C gives these first soluble derivatives of “circumnaphthalene”, one of the most stable mesophases known. The close contact of the large π systems within the columnar stacks and their good solubility makes these flexible disks promising tools for organic electronics.

    21. Synthesis of the C1–C26 Northern Portion of Azaspiracid-1: Kinetic versus Thermodynamic Control of the Formation of the Bis-spiroketal (pages 1787–1790)

      Xiao-Ti Zhou and Rich G. Carter

      Article first published online: 10 FEB 2006 | DOI: 10.1002/anie.200503733

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      North–South divide: An efficient synthesis of the entire C1–C26 (northern) portion of azaspiracid-1 is disclosed (see picture). Key transformations include the formation of a bis-spiroketal, the oxidation of a sulfone at C10 to form a β,γ-unsaturated ketone, a tandem Wadsworth–Emmons/hetero-Michael addition to construct ring D, and the highly selective hydroxylation at C20.

    22. Differences in and Comparison of the Catalytic Properties of Heme and Non-Heme Enzymes with a Central Oxo–Iron Group (pages 1790–1793)

      Sam P. de Visser

      Article first published online: 10 FEB 2006 | DOI: 10.1002/anie.200503841

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      Why so aggressive? Density functional calculations on the oxo–iron active species of dioxygenase and monooxygenase enzyme models show that the former ones are more aggressive catalysts with low reaction barriers. The differences are assigned to electronic factors, such as the electron transfer into a σ* anti-bonding Fe[BOND]O orbital and the reduction of the metal to an FeIII center in the rate-determining step.

    23. Syntheses, Structures, and Reactivity of Radial Oligocyclopentadienyl Metal Complexes: Penta(ferrocenyl)cyclopentadienyl and Congeners (pages 1794–1799)

      Yong Yu, Andrew D. Bond, Philip W. Leonard, K. Peter C. Vollhardt and Glenn D. Whitener

      Article first published online: 10 FEB 2006 | DOI: 10.1002/anie.200504047

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      “Supra”Cp: Fivefold Negishi coupling of pentaiodocymantrene resulted in radial oligocyclopentadienyl metal complexes (see scheme). These complexes show fascinating conformational and chemical behavior, including M[BOND]M and Cp[BOND]Cp bond formation and the liberation of the novel supraligand penta(ferrocenyl)cyclopentadiene. dba=dibenzylideneacetone.

    24. Donor–Acceptor Metallocene Catalysts for the Production of UHMW-PE: Pushing the Selectivity for Chain Growth to Its Limits (pages 1799–1803)

      K. Aleksander Ostoja Starzewski, Bruce S. Xin, Norbert Steinhauser, Johannes Schweer and Jordi Benet-Buchholz

      Article first published online: 10 FEB 2006 | DOI: 10.1002/anie.200504173

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      Plastic fantastic! Donor–acceptor zirconocenes with a donor (P)-substituted fluorenyl ligand and an acceptor (B)-substituted cyclopentadienyl ligand (see structure) are highly active ethylene polymerization catalysts that reveal an ultrahigh selectivity for chain propagation even at high temperatures, giving access to ultrahigh-molecular-weight polyethylenes (viscosity-average molecular weights Mη>1×106 g mol−1).

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      Towards Polymer-Based Hydrogen Storage Materials: Engineering Ultramicroporous Cavities within Polymers of Intrinsic Microporosity (pages 1804–1807)

      Neil B. McKeown, Bader Gahnem, Kadhum J. Msayib, Peter M. Budd, Carin E. Tattershall, Khalid Mahmood, Siren Tan, David Book, Henrietta W. Langmi and Allan Walton

      Article first published online: 10 FEB 2006 | DOI: 10.1002/anie.200504241

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      Three structurally diverse polymers of intrinsic microporosity reversibly adsorb significant quantities of hydrogen (1.4–1.7 % by mass at 77 K) and represent the first examples of a new type of purely organic hydrogen storage material, which can be tailored to meet the specific requirements of hydrogen physisorption.

    26. Colorimetric Screening of DNA-Binding Molecules with Gold Nanoparticle Probes (pages 1807–1810)

      Min Su Han, Abigail K. R. Lytton-Jean, Byung-Keun Oh, Jungseok Heo and Chad A. Mirkin

      Article first published online: 15 FEB 2006 | DOI: 10.1002/anie.200504277

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      Nanoparticle assemblies interconnected with DNA can be used to screen for DNA-binding molecules colorimetrically. The melting temperature of the nanoparticle assembly increases in the presence of strong-DNA-binding molecules. Thus, the strength of the DNA binding can be determined by the change in this sharp melting transition, which is observable by a blue-to-red color change (see picture).

    27. 3′-(2,4-Dinitrobenzenesulfonyl)-2′,7′-dimethylfluorescein as a Fluorescent Probe for Selenols (pages 1810–1813)

      Hatsuo Maeda, Kohei Katayama, Hiromi Matsuno and Tadayuki Uno

      Article first published online: 10 FEB 2006 | DOI: 10.1002/anie.200504299

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      Simply the BESThio: The fluorescein derivative BESThio (see scheme) operates as a thiol probe at pH 7.4 and functions as a selenol probe at pH 5.8, and can thus be selectively applied to the rapid quantification of selenocysteine and the determination of the selenocysteine content in selenoproteins such as glutathione peroxidase and thioredoxin reductase with high sensitivity.

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    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Book Review
    7. Highlight
    8. Review
    9. Communication
    10. Preview
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      Preview: Angew. Chem. Int. Ed. 11/2006 (page 1819)

      Article first published online: 1 MAR 2006 | DOI: 10.1002/anie.200690039

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