Chemistry - A European Journal

Cover image for Vol. 15 Issue 30

July 27, 2009

Volume 15, Issue 30

Pages 7255–7503

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
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    1. Cover Picture: Neutral Pentacoordinate Silicon(IV) Complexes with Silicon–Chalcogen (S, Se, Te) Bonds (Chem. Eur. J. 30/2009) (page 7255)

      Bastian Theis, Stefan Metz, Christian Burschka, Rüdiger Bertermann, Stefan Maisch and Reinhold Tacke

      Article first published online: 17 JUL 2009 | DOI: 10.1002/chem.200990111

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      Hard meets soft in pentacoordinate silicon(IV) complexes with soft chalcogen ligands that have been prepared and characterized by R. Tacke et al., as described in their Full Paper on page 7329 ff. These neutral pentacoordinate complexes are stable in the solid state and in solution.

  2. Graphical Abstract

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    3. Graphical Abstract
    4. Corrigendum
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    6. Concept
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    1. Graphical Abstract: Chem. Eur. J. 30/2009 (pages 7256–7263)

      Article first published online: 17 JUL 2009 | DOI: 10.1002/chem.200990112

  3. Corrigendum

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    3. Graphical Abstract
    4. Corrigendum
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    6. Concept
    7. Communications
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    1. You have free access to this content
      Reviewing the Polyolefin Cyclization Reaction of the C35 Polyprene Catalyzed by Squalene-Hopene Cyclase (page 7263)

      Tsutomu Hoshino, Yuko Kumai and Tsutomu Sato

      Article first published online: 17 JUL 2009 | DOI: 10.1002/chem.200990113

      This article corrects:

      Reviewing the Polyolefin Cyclization Reaction of the C35 Polyprene Catalyzed by Squalene-Hopene Cyclase

      Vol. 15, Issue 9, 2091–2100, Article first published online: 13 JAN 2009

  4. News

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    3. Graphical Abstract
    4. Corrigendum
    5. News
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  5. Concept

    1. Top of page
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    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
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    1. Asymmetric Catalysis

      Helical Chiral Pyridine N-Oxides: A New Family of Asymmetric Catalysts (pages 7268–7276)

      Jinshui Chen and Norito Takenaka

      Article first published online: 3 JUL 2009 | DOI: 10.1002/chem.200900607

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      Like a circle in a spiral: Described are advances in the design and development of chiral pyridine N-oxide catalysts for the enantioselective synthesis of chlorohydrins. Recently, helical chiral analogues (an example of which is shown here) have become available. The details of preparation and application of this new family of helical chiral catalysts are included.

  6. Communications

    1. Top of page
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    4. Corrigendum
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    1. Magnetic Properties

      Probing Lanthanide Anisotropy in Fe–Ln Aggregates by Using Magnetic Susceptibility Measurements and 57Fe Mössbauer Spectroscopy (pages 7278–7282)

      Muhammad Nadeem Akhtar, Valeriu Mereacre, Ghenadie Novitchi, Jean-Pierre Tuchagues, Christopher E. Anson and Annie K. Powell

      Article first published online: 27 JUN 2009 | DOI: 10.1002/chem.200900758

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      A great combination: The large uniaxial anisotropy of lanthanides and its influence on the local moments and spin-relaxation dynamics at the iron nuclei was probed by using 57Fe Mössbauer spectroscopy and magnetic susceptibility measurements (see picture). The derivation of the anisotropy was possible by comparing isomorphous clusters containing diamagnetic, isotropic, and anisotropic lanthanide ions.

    2. Cyclization

      Highly Regio- and Stereoselective Synthesis of Nine- to Twelve-Membered Cyclic Compounds by a Pd0-Catalyzed Cyclization Reaction between Allenes with a Nucleophilic Functionality and Organic Halides (pages 7283–7286)

      Xinpeng Jiang, Qing Yang, Yihua Yu, Chunling Fu and Shengming Ma

      Article first published online: 19 JUN 2009 | DOI: 10.1002/chem.200900972

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      Simple cyclization: A novel method has been developed for the highly regio- and stereoselective synthesis of nine- to twelve-membered cyclic compounds by a Pd0-catalyzed cyclization reaction of allenes with a carbon or nitrogen nucleophilic functionality. Oxidative addition and carbopalladation gave anti-π-allyl palladium intermediates, then an exclusive intramolecular nucleophilic attack at the terminal carbon atom of the allene moiety gave the E product in good yields (see scheme; Ts=tosyl; DMA=N,N-dimethylacetamide).

    3. Allenes

      Do Extremely Bent Allenes Exist? (pages 7287–7291)

      Mikko M. Hänninen, Anssi Peuronen and Heikki M. Tuononen

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200900928

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      Bent allenes: Theoretical calculations show that extremely bent allenes, cyclic or acyclic, adopt a ground state that only bears a formal relationship to classical allenes. Consequently, five-membered ring allenes favor a carbene-like electronic structure and formally contain a trivalent carbon(II) center (see figure).

    4. C[BOND]H Activation

      Direct Imidation to Construct 1H-Benzo[d]imidazole through PdII-Catalyzed C[BOND]H Activation Promoted by Thiourea (pages 7292–7296)

      Qing Xiao, Wen-Hua Wang, Gang Liu, Fan-Ke Meng, Jia-Hua Chen, Zhen Yang and Zhang-Jie Shi

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200900154

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      A new and straightforward method to construct 1H-benzo[d]imidazole was developed by means of PdII-catalyzed intramolecular C[BOND]H activation starting from easily available N-phenylbenzimidamide (see scheme). The detailed mechanism studies indicated that a palladacycle monomer or dimer is the key intermediate for this transformation and thiourea was used for the first time to promote the efficiency of C[BOND]H activation.

    5. Peptides

      Insights into the Geometrical Features Underlying β-O-GlcNAc Glycosylation: Water Pockets Drastically Modulate the Interactions between the Carbohydrate and the Peptide Backbone (pages 7297–7301)

      Alberto Fernández-Tejada, Francisco Corzana, Jesús H. Busto, Gonzalo Jiménez-Osés, Jesús Jiménez-Barbero, Alberto Avenoza and Jesús M. Peregrina

      Article first published online: 19 JUN 2009 | DOI: 10.1002/chem.200901204

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      Water pockets at key sites as well as specific hydrogen bonds modulate sugar–peptide interactions in β-N-acetyl-D-glucosamine (β-O-GlcNAc) glycopeptides (see picture). It is likely that these solvent pockets have important biological implications, providing the required presentation of the GlcNAc moieties to interact with their biological receptors.

    6. Asymmetric Catalysis

      Matching and Mismatching Effects of Hybrid Chiral Biaxial Bisphosphine Ligands in Enantioselective Hydrogenation of Ketoesters (pages 7302–7305)

      Xianfeng Sun, Wei Li, Le Zhou and Xumu Zhang

      Article first published online: 25 JUN 2009 | DOI: 10.1002/chem.200900722

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      Highly enantioselective hydrogenation reactions provide facile access to optically active α- and β-hydroxy acid derivatives (see scheme), which are very important chiral building blocks for the syntheses of a variety of natural products and biologically active molecules. The selectivity data revealed that the matched ligand system was L*, which afforded much higher enantioselectivities in hydrogenation of β-ketoesters and methyl benzoylformate.

    7. Fullerene Chemistry

      A Click–Click Approach for the Preparation of Functionalized [5:1]-Hexaadducts of C60 (pages 7306–7309)

      Julien Iehl and Jean-François Nierengarten

      Article first published online: 3 JUL 2009 | DOI: 10.1002/chem.200901291

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      Successive attachment: The paper describes a C60 hexaadduct bearing ten azides and two TMS-protected alkyne groups allowing the successive attachment of ten alkyne building blocks (in blue) and two azide units (in red) through successive click reactions.

  7. Full Papers

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    9. Preview
    1. Enzyme Catalysis

      Dihydroxyacetone Phosphate Aldolase Catalyzed Synthesis of Structurally Diverse Polyhydroxylated Pyrrolidine Derivatives and Evaluation of their Glycosidase Inhibitory Properties (pages 7310–7328)

      Jordi Calveras, Meritxell Egido-Gabás, Livia Gómez, Josefina Casas, Teodor Parella, Jesús Joglar, Jordi Bujons and Pere Clapés

      Article first published online: 3 JUL 2009 | DOI: 10.1002/chem.200900838

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      Aldolase-assisted diversity oriented synthesis: L-Fuculose- and L-rhamnulose-1-phosphate aldolases (FucA, RhuA) from E. coli are key biocatalysts for the generation of a collection of structurally diverse pyrrolidine-type iminosugars from DHAP and N-Cbz-2-aminoaldehyde derivatives (see figure). Evaluation against a panel of glycosidases allowed the identification of strong-to-moderate inhibitors. Computational models substantiate our experimental observations on aldolase reactivity and iminosugar activity.

    2. Silicon Chemistry

      Neutral Pentacoordinate Silicon(IV) Complexes with Silicon–Chalcogen (S, Se, Te) Bonds (pages 7329–7338)

      Bastian Theis, Stefan Metz, Christian Burschka, Rüdiger Bertermann, Stefan Maisch and Reinhold Tacke

      Article first published online: 3 JUL 2009 | DOI: 10.1002/chem.200900592

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      A bunch of softies! Neutral pentacoordinate silicon(IV) complexes with SiS2ONC, SiSeSONC, SiTeSONC (A), SiSe2O2C, SiSe2S2C, and SiSe4C (B) skeletons have been synthesized and structurally characterized by using X-ray crystallography and solid- and solution-state NMR spectroscopy.

    3. Cationic Ligands

      Cationic Heterocycles as Ligands: Synthesis and Reactivity with Anionic Nucleophiles of Cationic Triruthenium Clusters Containing C-Metalated N-Methylquinoxalinium or N-Methylpyrazinium Ligands (pages 7339–7349)

      Javier A. Cabeza, Ignacio del Río, María C. Goite, Enrique Pérez-Carreño and Vanessa Pruneda

      Article first published online: 19 JUN 2009 | DOI: 10.1002/chem.200901079

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      Easy target: Triruthenium clusters that have cationic N-heterocyclic ligands are easily attacked by nucleophiles at a carbon atom of the heterocyclic ligand (see scheme; R=Me, H). These reactions, which are orbital-controlled rather than charge-controlled, give products that contain neutral nonaromatic N-heterocyclic ligands.

    4. Bioinorganic Chemistry

      Structural Adaptability of Zinc Binding Sites: Different Structures in Partially, Fully, and Heavy-Metal Loaded States (pages 7350–7358)

      Uwe Heinz, Lars Hemmingsen, Martin Kiefer and Hans-Werner Adolph

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200900870

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      The structural space accessible to zinc fingers depends on the nature of the bound metal ions and the metal-to-protein stoichiometry (see figure). Metal-bridged species were observed by perturbed angular correlation (PAC), EXAFS, and stopped-flow UV/Vis spectroscopy. The observed structural diversity might represent essential features of metal-ion-mediated protein–protein interactions and metal-ion transfer.

      Corrected by:

      Corrigendum: Structural Adaptability of Zinc Binding Sites: Different Structures in Partially, Fully, and Heavy-Metal Loaded States

      Vol. 15, Issue 35, 8664, Article first published online: 1 SEP 2009

    5. Carbon Nanotubes

      Electron-Transfer Kinetics of Microperoxidase-11 Covalently Immobilised onto the Surface of Multi-Walled Carbon Nanotubes by Reactive Landing of Mass-Selected Ions (pages 7359–7367)

      Franco Mazzei, Gabriele Favero, Marco Frasconi, Alessandra Tata and Federico Pepi

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200900887

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      Soft-landing takes off: A novel approach to the highly selective covalent binding of a redox protein, microperoxidase-11 (MP-11), to multi-walled carbon nanotube (MWCNT) electrodes by soft-landing mass-selected ions is presented (see figure), perhaps forging a path toward next-generation biocomponents.

    6. Reaction Optimization

      High-Throughput Reaction Optimisation and Activity Screening of Ferrocene-Based Lewis Acid–Catalyst Complexes by Using Continuous-Flow Reaction Detection Mass Spectrometry (pages 7368–7375)

      Cornelius T. Martha, Anton Heemskerk, Jan-Carel Hoogendoorn, Niels Elders, Wilfried M. A. Niessen, Romano V. A. Orru and Hubertus Irth

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200900317

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      Maximum efficiency! A high-throughput reaction detection system, in which reactant conversion and product determination are integrated into a single comprehensive system, is presented (see figure). It is capable of quickly optimising reaction conditions and screening for optimal homogenous catalysts for a selected synthetic conversion and can be used to assess activity in different solvents.

    7. Heterocycles

      Solvent-Enhanced Diastereo- and Regioselectivity in the PdII-Catalyzed Synthesis of Six- and Eight-Membered Heterocycles via cis-Aminopalladation (pages 7376–7381)

      Árpád Balázs, Anasztázia Hetényi, Zsolt Szakonyi, Reijo Sillanpää and Ferenc Fülöp

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200900477

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      Oxidative amination: The PdII-catalyzed intramolecular oxidative cyclization of tosyl-protected cis- and trans-N-allyl-2-aminocyclohexanecarboxamides was examined, and efficient syntheses of cyclohexane-fused pyrimidin-4-ones and 1,5-diazocin-6-ones were developed (see scheme; HG 2nd = Hoveyda–Grubbs 2nd generation catalyst).

    8. Triplet States

      Selective Triplet-State Formation during Charge Recombination in a Fullerene/Bodipy Molecular Dyad (Bodipy=Borondipyrromethene) (pages 7382–7393)

      Raymond Ziessel, Ben D. Allen, Dorota B. Rewinska and Anthony Harriman

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200900440

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      Which electron transfer? The title compound (see figure) undergoes a variety of light-induced energy- and electron-transfer events, according to the polarity of the solvent. Triplet states resident on the two terminals are almost isoenergetic, but charge recombination leads exclusively to population of the C60-based triplet state.

    9. Reaction Mechanisms

      The Catalytic Mechanism of Fluoroacetate Dehalogenase: A Computational Exploration of Biological Dehalogenation (pages 7394–7403)

      Takashi Kamachi, Tomonori Nakayama, Osamu Shitamichi, Keiji Jitsumori, Tatsuo Kurihara, Nobuyoshi Esaki and Kazunari Yoshizawa

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200801813

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      Measuring the mechanics: Quantum mechanical/molecular mechanical calculations were carried out to obtain better information about structural and catalytic interactions in the binding site of fluoroacetate dehalogenase by using the crystal structure of the enzyme from Burkholderia sp. FA1 (see graphic).

    10. Anion Recognition

      Polydiacetylene-Based Colorimetric Self-Assembled Vesicular Receptors for Biological Phosphate Ion Recognition (pages 7404–7412)

      D. Amilan Jose, Stefan Stadlbauer and Burkhard König

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200900339

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      Nanosensors: Self-assembled vesicular polydiacetylene (PDA) particles with embedded metal complex receptor sites have been prepared. Addition of ATP and PPi to the PDA vesicle solution induces a color change from blue to red observable by the naked eye (see figure). Other anions failed to induce any spectral changes.

    11. Cluster Compounds

      Modelling the Magnetic Behaviour of Square-Pyramidal CoII5 Aggregates: Tuning SMM Behaviour through Variations in the Ligand Shell (pages 7413–7422)

      Frederik Klöwer, Yanhua Lan, Joscha Nehrkorn, Oliver Waldmann, Christopher E. Anson and Annie K. Powell

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200900101

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      Anything but trivial: Three CoII5 compounds with similar square-pyramidal core structures (an example is shown here) show markedly different magnetic behaviours as a result of small changes in the ligand shell by modifying the magnitude of exchange constants, affecting the J and g matrices in a non-trivial way.

    12. Fullerenes

      Large Di- and Heptafullerene Polyelectrolytes Composed of C60 Building Blocks Having a Highly Symmetrical Hexakisaddition Pattern (pages 7423–7433)

      Patrick Witte, Frank Hörmann and Andreas Hirsch

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200900319

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      A giant heptafullerene (see picture) is one of three new prototypes of large fullerene-based polyelectrolytes with a highly symmetrical hexakisaddition pattern, obtained by template-mediated synthesis. It can store up to 60 positive charges in its periphery, and is the largest molecular polyelectrolyte with a defined three-dimensional structure.

    13. Supramolecular Architectures

      Synthesis and Orthogonal Functionalization of [60]Fullerene e,e,e-Trisadducts with Two Spherically Defined Addend Zones (pages 7434–7446)

      Florian Beuerle and Andreas Hirsch

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200900329

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      Tailor-made: Supramolecular building blocks are realized through the efficient tether-directed synthesis and functionalization of [60]fullerene to give a novel family of e,e,e-trisadducts (see picture). These adducts bear two orthogonal sets of addends that are spherically well arranged and affect the chemical and physical properties of these fullerene derivatives in different ways.

    14. Synthesis of Amphiphilic [60]Fullerene [3:3]Hexakisadducts with Four Spherically Defined Addend Zones (pages 7447–7455)

      Florian Beuerle and Andreas Hirsch

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200900330

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      Step by step… a stepwise tether-directed synthesis of [3:3]hexakisadducts affords the synthesis of highly functionalized [60]fullerene hexakisadducts with up to four independently addressable addend zones. A series of analogous amphiphiles can be synthesized by a systematic introduction of both hydrophilic and lipophilic moieties in specific addend zones (see picture).

    15. Lanthanide-Binding Peptides

      Lanthanide(III) Complexes with Two Hexapeptides Incorporating Unnatural Chelating Amino Acids: Secondary Structure and Stability (pages 7456–7469)

      Federico Cisnetti, Christelle Gateau, Colette Lebrun and Pascale Delangle

      Article first published online: 27 JUN 2009 | DOI: 10.1002/chem.200900747

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      How structure tunes stability: Two unnatural amino acids bearing aminodiacetate groups have been introduced into peptide sequences to obtain efficient hexadentate lanthanide-binding peptides. The most compact LnP2 complex benefits from secondary structure elements, namely a β-turn and a hydrophobic Trp–Pro interaction, which evidence the non-innocent character of the peptide spacer in stabilizing the coordination complex (see figure).

    16. Stereochemistry

      Stereochemistry of Compounds with Coordination Number Ten (pages 7470–7480)

      Antonio Ruiz-Martínez and Santiago Alvarez

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200900547

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      Ten out of ten: The coordination polyhedra adopted by ten-coordinated metal centers in more than 500 crystal structures are systematically studied by means of continuous shape measures and the resulting trends are summarized in a shape atlas. The picture shows a pentagonal antiprismatic structure.

    17. Artificial Enzymes

      Noncovalent Modulation of pH-Dependent Reactivity of a Mn–Salen Cofactor in Myoglobin with Hydrogen Peroxide (pages 7481–7489)

      Jun-Long Zhang, Dewain K. Garner, Lei Liang, David A. Barrios and Yi Lu

      Article first published online: 25 JUN 2009 | DOI: 10.1002/chem.200802449

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      Biosynthetic model: To demonstrate the protein modulation of metal-cofactor reactivity through noncovalent interactions, pH-dependent sulfoxidation and 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) oxidation reactivity of a designed myoglobin (Mb) containing non-native Mn–salen complex (1) was investigated by using H2O2 as the oxidant.

    18. Heterogeneous Catalysis

      Heterogeneous Wheel-Shaped Cu20-Polyoxotungstate [Cu20Cl(OH)24(H2O)12(P8W48O184)]25− Catalyst for Solvent-Free Aerobic Oxidation of n-Hexadecane (pages 7490–7497)

      Lifang Chen, Juncheng Hu, Sib Sankar Mal, Ulrich Kortz, Helge Jaensch, Georges Mathys and Ryan M. Richards

      Article first published online: 23 JUN 2009 | DOI: 10.1002/chem.200900031

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      Solvent-free aerobic oxidation: The supported wheel-shaped polyanion [Cu20Cl(OH)24(H2O)12(P8W48O184)]25− is an excellent heterogeneous catalyst for the solvent-free aerobic oxidation of n-hexadecane to alcohols and ketones by using air as the oxidant under ambient conditions as a green process, with an exceptionally high turnover frequency of 20 000 h−1 through a classical free-radical chain autoxidation mechanism.

  8. Preview

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    9. Preview
    1. You have free access to this content
      Preview: Chem. Eur. J. 31/2009 (page 7503)

      Article first published online: 17 JUL 2009 | DOI: 10.1002/chem.200990115

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