Chemistry - A European Journal

Cover image for Vol. 14 Issue 3

January 18, 2008

Volume 14, Issue 3

Pages 771–1051

  1. Cover Picture

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    1. Cover Picture: Hypervalent Silicon versus Carbon: Ball-in-a-Box Model (Chem. Eur. J. 3/2008) (page 771)

      Simon C. A. H. Pierrefixe, Célia Fonseca Guerra and F. Matthias Bickelhaupt

      Version of Record online: 10 JAN 2008 | DOI: 10.1002/chem.200890001

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      Size matters when considering if a group 14 atom (A=silicon or carbon) can form stable, hypervalent [Cl[BOND]AH3[BOND]Cl] structures or not. In their Full Paper on page 819 ff., F. M. Bickelhaupt et al. present the ball-in-a-box model that shows how silicon fits perfectly into the box formed by the substituents, whereas carbon is too small and “drops to the bottom”.

  2. Graphical Abstract

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  3. Corrigendum

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      Structural Importance of Secondary Interactions in Molecules: Origin of Unconventional Conformations of Phosphine–Borane Adducts (page 779)

      Patrick Spies, Roland Fröhlich, Gerald Kehr, Gerhard Erker and Stefan Grimme

      Version of Record online: 10 JAN 2008 | DOI: 10.1002/chem.200890003

      This article corrects:
  4. News

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  5. Concepts

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    1. Extrahelical Damaged Base Recognition by DNA Glycosylase Enzymes (pages 786–793)

      James T. Stivers

      Version of Record online: 15 NOV 2007 | DOI: 10.1002/chem.200701501

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      Extrahelical base recognition is a conserved strategy used by DNA repair enzymes to distinguish between right and wrong bases in the genome. The process involves an extraordinary conformational change in the DNA that may be initiated by spontaneous thermally induced “breathing motions” of DNA base pairs (see graphic).

    2. Decrypting the TEM Images for Deciphering the Microstructural Code of Complex Oxides (pages 794–805)

      Maryvonne Hervieu, Christine Martin, Olivier Pérez, Richard Retoux and Sylvie Malo

      Version of Record online: 14 DEC 2007 | DOI: 10.1002/chem.200701023

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      A strategy to realize materials design is the research of “signatures” of the different structural levels existing in the complex materials (an example of which is shown here), by using transmission electron microscopy. The challenge is to achieve an accurate interpretation of these signals and, having this code, to obtain the bases for discovering novel materials and tuning their specific properties.

  6. Full Papers

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    1. In an Attempt to Provide a User's Guide to the Galaxy of Benzylidene, Alkoxybenzylidene, and Indenylidene Ruthenium Olefin Metathesis Catalysts (pages 806–818)

      Michał Bieniek, Anna Michrowska, Dmitry L. Usanov and Karol Grela

      Version of Record online: 6 DEC 2007 | DOI: 10.1002/chem.200701340

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      “First… Don't Panic” The data reported in this paper demonstrate the difficulty in anticipating the activity of pre-catalysts with respect to a specific substrate and highlight that, unfortunately, different catalysts prove to be optimal for different applications and no single catalyst outperforms all others in all cases. Nevertheless, some generalisations on structure–activity relationships can be made.

    2. Hypervalent Silicon versus Carbon: Ball-in-a-Box Model (pages 819–828)

      Simon C. A. H. Pierrefixe, Célia Fonseca Guerra and F. Matthias Bickelhaupt

      Version of Record online: 4 DEC 2007 | DOI: 10.1002/chem.200701252

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      Ball-in-a-box model: Based on molecular orbital (MO) theoretical analyses, we show how the inability or ability of a group 14 atom (A) to form a stable hypervalent structure [Cl[BOND]AH3[BOND]Cl] can be straightforwardly understood in terms of the ball-in-a-box model (illustrated here) presented in this study.

    3. Highly Efficient Total Synthesis of the Marine Natural Products (+)-Avarone, (+)-Avarol, (−)-Neoavarone, (−)-Neoavarol and (+)-Aureol (pages 829–837)

      Junji Sakurai, Takamasa Oguchi, Kazuhiro Watanabe, Hideki Abe, Syu-ichi Kanno, Masaaki Ishikawa and Tadashi Katoh

      Version of Record online: 8 NOV 2007 | DOI: 10.1002/chem.200701386

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      Marine natural products: (+)-Avarone, (+)-avarol, (−)-neoavarone, (−)-neoavarol, and (+)-aureol have been efficiently synthesized in enantiomerically pure forms starting from the known bicyclic enone (31–41 % overall yields in 7–10 steps). The cell growth inhibition assay showed novel aspects of the structure–activity relationships for the development of new anticancer agents.

    4. Bisamides Derived from Azulene-1,3- and -5,7-dicarboxylic Acids as New Building Blocks for Anion Receptors (pages 838–846)

      Tomasz Zieliński, Mariusz Kȩdziorek and Janusz Jurczak

      Version of Record online: 20 SEP 2007 | DOI: 10.1002/chem.200700592

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      Azulene in anion recognition: Bisamides based on the azulene moiety were investigated as building blocks for anion receptors. The derivatives of azulene-5,7-dicarboxylic acid (shown here) have a binding cleft complementary to the chloride anion.

    5. Site Selectivity in the Reactions of the Hexanuclear Platinum Cluster [Pt6(μ-PtBu2)4(CO)6][CF3SO3]2 (pages 847–856)

      Cristina Bonaccorsi, Fabrizia Fabrizi de Biani, Piero Leoni, Fabio Marchetti, Lorella Marchetti and Piero Zanello

      Version of Record online: 28 SEP 2007 | DOI: 10.1002/chem.200700765

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      New cluster synthons: A series of derivatives [Pt6(μ-PtBu2)4(CO)4XY][CF3SO3]n (where X,Y=halide, H, CHO, COOMe then n=0, or if X,Y=C, P, N neutral ligand then n=2) are useful precursors for the synthesis of clusters containing ordered structures (see figure) and many of them have been prepared and characterized. All complexes display two reversible one-electron reduction steps.

    6. Development of a Series of Cross-Linking Agents that Effectively Stabilize α-Helical Structures in Various Short Peptides (pages 857–863)

      Kazuhisa Fujimoto, Masaoki Kajino and Masahiko Inouye

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/chem.200700843

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      Stable α-helical structures in short peptides: A variety of cross-linking agents intended to stabilize helical structures in short peptides have been developed, and the helical content of the resulting cross-linked peptides were analyzed in detail by circular dichroism. We found combinations suitable for the formation of stable helical structures between each of the peptides and the cross-linking agents.

    7. Sequence-Specific Alkylation by Y-Shaped and Tandem Hairpin Pyrrole–Imidazole Polyamides (pages 864–870)

      Shunta Sasaki, Toshikazu Bando, Masafumi Minoshima, Ken-ichi Shinohara and Hiroshi Sugiyama

      Version of Record online: 14 NOV 2007 | DOI: 10.1002/chem.200700571

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      New design of alkylating polyamides: Minor-groove-binding Y-shaped and tandem hairpin polyamides that are composed of N-methylpyrrole, N-methylimidazole, and an alkylating unit were developed (see figure). An investigation using high-resolution gel electrophoresis revealed that the Y-shaped and tandem hairpin polyamides preferentially alkylated at adenine of the targeted 10 bp and 8 bp matching sequences, respectively.

    8. Supramolecular Helical Columns from the Self-Assembly of Chiral Rods (pages 871–881)

      Ja-Hyoung Ryu, Lijun Tang, Eunji Lee, Ho-Joong Kim and Myongsoo Lee

      Version of Record online: 1 OCT 2007 | DOI: 10.1002/chem.200701080

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      Chiral template: When an opened chiral-bridged rod molecule was added to a solution of closed chiral-bridged rod molecules, both molecules co-assemble into a one-handed helical structure owing to conformational flexibility of the opened chiral-bridged rod molecule (see picture).

    9. Organic–Inorganic Hybrid Polymer-Encapsulated Magnetic Nanobead Catalysts (pages 882–885)

      Takayoshi Arai, Toru Sato, Hirofumi Kanoh, Katsumi Kaneko, Koichi Oguma and Akira Yanagisawa

      Version of Record online: 12 NOV 2007 | DOI: 10.1002/chem.200701371

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      Attractive beads: An organic–inorganic hybrid polymer of {[Cu(bpy)(BF4)2(H2O)2](bpy)}n (bpy=4,4′-bipyridine) was constructed on the surface of magnetic beads and the resulting hybrid-polymer-encapsulated beads were utilized as catalysts for the oxidation of silyl enolates to provide the corresponding α-hydroxy carbonyl compounds in high yield (see picture).

    10. Stereoselective Isomerisation of N-Allyl Aziridines into Geometrically Stable Z Enamines by Using Rhodium Hydride Catalysis (pages 886–894)

      Derek S. Tsang, Sharon Yang, France-Aimée Alphonse and Andrei K. Yudin

      Version of Record online: 8 NOV 2007 | DOI: 10.1002/chem.200701322

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      KineticZenamines: Isomerisation of N-allylaziridines with rhodium(I) hydride is believed to proceed via a five-membered intermediate, which forces Z enamine geometry as a kinetic product (see scheme). This behaviour is unique to aziridines and is not observed with other tertiary amines, which instead undergo hydride addition and β-hydride elimination to form thermodynamically favoured E enamines.

    11. Enantio- and Diastereoselective Synthesis of Duocarmycine-Based Prodrugs for a Selective Treatment of Cancer by Epoxide Opening (pages 895–901)

      Lutz F. Tietze, Heiko J. Schuster, Sonja M. Hampel, Stephan Rühl and Roland Pfoh

      Version of Record online: 21 NOV 2007 | DOI: 10.1002/chem.200700988

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      A key to the puzzle: A highly efficient enantio- and diastereoselective synthesis of 2 starting from 1 has been developed. Compound 2 is a key intermediate in the preparation of prodrugs such as 3, which may be highly suitable for a selective treatment of cancer by using the antibody-directed enzyme prodrug therapy approach.

    12. A Promising Method for Phosphinidene Generation: Complexes of Phosphinidenes with N-Donor ligands (pages 902–908)

      Zoltán Benkõ, Dietrich Gudat and László Nyulászi

      Version of Record online: 22 OCT 2007 | DOI: 10.1002/chem.200701077

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      Phosphinidenes from N-heterocycles: The generation of phosphinidenes from N-heterocycles (see scheme) forming N-donor leaving groups is shown computationally to be a feasible synthetic possibility.

    13. Thixotropic Twin-Dendritic Organogelators (pages 909–918)

      Virgil Percec, Mihai Peterca, Michael E. Yurchenko, Jonathan G. Rudick and Paul A. Heiney

      Version of Record online: 19 NOV 2007 | DOI: 10.1002/chem.200701273

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      To gel and back again: Twin-dendritic organogelators self-assemble in bulk to form self-organized arrays and in solution to gel organic solvents. Several examples of thixotropic gels, wherein the gel recovers its elasticity after being subjected to shear, are reported. The self-assembly process and resulting gel properties are dictated by hydrogen bonding within cylindrical objects (see top view of molecular model). Porous columnar assemblies are found to favor thixotropic-gel formation.

    14. Complexation of the Vulcanization Accelerator Tetramethylthiuram Disulfide and Related Molecules with Zinc Compounds Including Zinc Oxide Clusters (Zn4O4) (pages 919–932)

      Ralf Steudel, Yana Steudel and Ming Wah Wong

      Version of Record online: 12 NOV 2007 | DOI: 10.1002/chem.200701089

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      Spontaneous S−S dissociation of the vulcanization accelerator tetramethylthiuram disulfide (TMTD) is predicted to occur on coordination to zinc ions or zinc oxide under working conditions. According to DFT and ab initio calculations the dissociation products form very stable chelate complexes with zinc oxide which are proposed to be key reagents in rubber vulcanization accelerated by zinc compounds. The picture shows a complex of TMTD with Zn4O4 as a model of a zinc oxide surface (C black, H white, N blue, S yellow Zn light blue).

    15. Cationic Bis-cyclometallated Iridium(III) Phenanthroline Complexes with Pendant Fluorenyl Substituents: Synthesis, Redox, Photophysical Properties and Light-Emitting Cells (pages 933–943)

      Xianshun Zeng, Mustafa Tavasli, Igor F. Perepichka, Andrei S. Batsanov, Martin R. Bryce, Chien-Jung Chiang, Carsten Rothe and Andrew P. Monkman

      Version of Record online: 21 NOV 2007 | DOI: 10.1002/chem.200700308

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      Illuminating chemistry: A series of cationic cyclometallated IrIII complexes of general formula [Ir(ppy)2(phen)]PF6 (ppy=2-phenylpyridine, phen=a substituted phenanthroline; for example, see picture) have been synthesised and their photophysical and electrochemical properties characterised. Spin-coated light-emitting cells (LECs) have been fabricated and the devices have been operated in air with no reduction in efficiency after storage for one week in air.

    16. Screening of a Phosphite–Phosphoramidite Ligand Library for Palladium-Catalysed Asymmetric Allylic Substitution Reactions: The Origin of Enantioselectivity (pages 944–960)

      Oscar Pàmies and Montserrat Diéguez

      Version of Record online: 2 NOV 2007 | DOI: 10.1002/chem.200700852

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      A new library of readily available highly modular phosphite–phosphoramidite ligands (see picture) for asymmetric palladium-catalysed allylic substitution reactions has been prepared in one step from commercially available chiral 1,2-amino alcohols. This ligand library affords high reaction rates (TOFs of up to 800 mol (mol h)−1) and enantioselectivities (ees of up to 99 %) and contains a broad range of disubstituted hindered and unhindered substrate types.

    17. Zr-TUD-1: A Lewis Acidic, Three-Dimensional, Mesoporous, Zirconium-Containing Catalyst (pages 961–972)

      Anand Ramanathan, M. Carmen Castro Villalobos, Cees Kwakernaak, Selvedin Telalovic and Ulf Hanefeld

      Version of Record online: 8 NOV 2007 | DOI: 10.1002/chem.200700725

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      Versatile catalyst: The three-dimensional, mesoporous Zr-TUD-1 is a versatile catalyst for Lewis acid catalysed reactions (see scheme). It displayed activity in the Meerwein–Ponndorf–Verley reduction and was particularly active in the C[BOND]C bond forming Prins reaction. Recycling experiments proved unequivocally that Zr-TUD-1 is a very stable, recyclable, heterogeneous catalyst.

    18. Stable Silanetriols That Contain tert-Alkoxy Groups: Versatile Precursors of Siloxane-Based Nanomaterials (pages 973–980)

      Jumpei Suzuki, Atsushi Shimojima, Yasuhiro Fujimoto and Kazuyuki Kuroda

      Version of Record online: 8 NOV 2007 | DOI: 10.1002/chem.200700914

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      Dual functions oftert-alkoxy groups: Novel tert-alkoxysilanetriols (ROSi(OH)3, R=adamantyl and 3-ethyl-3-pentyl) have successfully been used as molecular building blocks to produce ordered siloxane-based nanomaterials. tert-Alkoxy groups serve not only as protecting groups of siloxane species, but also as templates to generate micropores to provide unique synthetic pathways for the design of ordered silica-based materials (see figure).

    19. An Anthracene-Based Photochromic Macrocycle as a Key Ring Component To Switch a Frequency of Threading Motion (pages 981–986)

      Keiji Hirose, Yoshinobu Shiba, Kazuaki Ishibashi, Yasuko Doi and Yoshito Tobe

      Version of Record online: 12 NOV 2007 | DOI: 10.1002/chem.200701291

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      Switching device: A switching in frequency of threading motion (see scheme) is described by using a pseudorotaxane system that consists of dibenzylammonium hexafluorophosphate and a [24]crown-8-type macrocycle that contains a photochromic dianthrylethane.

    20. A Gd3+-Based Magnetic Resonance Imaging Contrast Agent Sensitive to β-Galactosidase Activity Utilizing a Receptor-Induced Magnetization Enhancement (RIME) Phenomenon (pages 987–995)

      Kenjiro Hanaoka, Kazuya Kikuchi, Takuya Terai, Toru Komatsu and Tetsuo Nagano

      Version of Record online: 8 NOV 2007 | DOI: 10.1002/chem.200700785

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      Monitoring β-galactosidase-activity: A novel β-galactosidase-activated MRI contrast agent, 1, was developed which is based on the receptor-induced magnetization enhancement (RIME) approach. The compound 1 exhibits an increase in the r1 relaxivity in response to β-galactosidase activity by binding to the macromolecule, human serum albumin (HSA) (see picture). The binding of an MRI contrast agent to a macromolecule substantially slows molecular rotation of the Gd3+ complex.

    21. Environmentally Friendly Chemoselective Oxidation of Primary Aliphatic Amines by Using a Biomimetic Electrocatalytic System (pages 996–1003)

      Martine Largeron, Angèle Chiaroni and Maurice-Bernard Fleury

      Version of Record online: 8 NOV 2007 | DOI: 10.1002/chem.200700876

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      Chemoselective oxidation of primary aliphatic amines to imines has been successfully achieved under metal-free conditions by using diverse electrogenerated o-azaquinone mediators. The catalytic efficiency of these amine oxidase mimics strongly depends on the nature of the substituents R and R′.

    22. Intramolecular Alkyl Phosphine Dehydrogenation in Cationic Rhodium Complexes of Tris(cyclopentylphosphine) (pages 1004–1022)

      Thomas M. Douglas, Simon K. Brayshaw, Romaeo Dallanegra, Gabriele Kociok-Köhn, Stuart A. Macgregor, Gemma L. Moxham, Andrew S. Weller, Tebikie Wondimagegn and Prabha Vadivelu

      Version of Record online: 8 NOV 2007 | DOI: 10.1002/chem.200700954

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      The concise dehydrogenation of tris(cyclopentylphosphine), with or without a hydrogen acceptor, to form hybrid phosphine–alkene ligands is described (see scheme) and modelled for a range of cationic rhodium systems.

    23. Asymmetric Iodocyclization Catalyzed by Salen–CrIIICl: Its Synthetic Application to Swainsonine (pages 1023–1028)

      Hyo Young Kwon, Chul Min Park, Sung Bae Lee, Joo-Hack Youn and Sung Ho Kang

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/chem.200701199

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      Enantioselective iodocyclization: Catalytic enantioselective iodocyclization of γ-hydroxy-cis-alkenes has been established using iodine in the presence of 7 mol % of (R,R)-salen–CrIIICl complex activated by 0.7 equivalents of N-chlorosuccinimide to provide 2-substituted tetrahydrofurans with 74 to 93 % ee (see scheme). Its synthetic application has consummated asymmetric synthesis of an indolizidine alkaloid, swainsonine.

    24. Revealing Phenylium, Phenonium, Vinylenephenonium, and Benzenium Ions in Solution (pages 1029–1039)

      Ilse Manet, Sandra Monti, Gottfried Grabner, Stefano Protti, Daniele Dondi, Valentina Dichiarante, Maurizio Fagnoni and Angelo Albini

      Version of Record online: 14 NOV 2007 | DOI: 10.1002/chem.200701043

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      In a flash! The 4-methoxyphenylium ion (1+) has been generated in the triplet state by photolysis of 4-chloroanisole in polar media and detected by flash photolysis (λmax=400 nm). Addition of alkenes and aromatics yielded further cations that were characterized.

    25. Investigation of Hydrogen Physisorption Active Sites on the Surface of Porous Carbonaceous Materials (pages 1040–1046)

      Deyang Qu

      Version of Record online: 12 NOV 2007 | DOI: 10.1002/chem.200701042

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      Hydrogen binding gets edgy: The active site for hydrogen physisorption is the edge orientation of defective graphene sheets. Hydrogen-specific physisorption increases with increasing R value, in which R is the relative amount of edge orientation in carbon materials (see graph).

  7. Preview

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concepts
    7. Full Papers
    8. Preview
    1. You have free access to this content
      Preview: Chem. Eur. J. 4/2008 (page 1051)

      Version of Record online: 10 JAN 2008 | DOI: 10.1002/chem.200890000

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