Chemistry - A European Journal

Cover image for Vol. 14 Issue 31

October 29, 2008

Volume 14, Issue 31

Pages 9451–9795

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    9. Preview
    1. Cover Picture: Stereoselective Glycal Fluorophosphorylation: Synthesis of ADP-2-fluoroheptose, an Inhibitor of the LPS Biosynthesis (Chem. Eur. J. 31/2008) (page 9451)

      Hirofumi Dohi, Régis Périon, Maxime Durka, Michael Bosco, Yvain Roué, François Moreau, Sylvestre Grizot, Arnaud Ducruix, Sonia Escaich and Stéphane P. Vincent

      Article first published online: 21 OCT 2008 | DOI: 10.1002/chem.200890123

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      From selectfluor chemistry to the crystal structure of a bacterial enzyme implied in the lipopolysaccharide (LPS) biosynthesis. In their Full Paper on page 9530 ff., S. P. Vincent et al. describe the development of a β-stereoselective fluorophosphorylation methodology and the synthesis of a challenging nucleoside diphosphate-sugar analogue of an important intermediate of the LPS biosynthesis.

  2. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Concept
    7. Communications
    8. Full Papers
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    1. Graphical Abstract: Chem. Eur. J. 31/2008 (pages 9452–9463)

      Article first published online: 21 OCT 2008 | DOI: 10.1002/chem.200890124

  3. Corrigenda

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    9. Preview
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      One-Pot Oxidative Esterification and Amidation of Aldehydes (page 9463)

      Kekeli Ekoue-Kovi and Christian Wolf

      Article first published online: 21 OCT 2008 | DOI: 10.1002/chem.200890128

      This article corrects:

      One-Pot Oxidative Esterification and Amidation of Aldehydes

      Vol. 14, Issue 21, 6302–6315, Article first published online: 3 JUN 2008

  4. News

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Concept
    7. Communications
    8. Full Papers
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  5. Concept

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Concept
    7. Communications
    8. Full Papers
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    1. Solid-Phase Synthesis

      Solid-Phase Synthesis of Transition-Metal Complexes (pages 9468–9480)

      Katja Heinze, Manuela Beckmann and Klaus Hempel

      Article first published online: 9 JUL 2008 | DOI: 10.1002/chem.200800697

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      It also works with metals! Solid-phase synthesis procedures have been used to selectively construct linear, oligonuclear transition-metal complexes with precise length, sequence and direction (see scheme). Two synthetic strategies are described: formation of coordinative bonds or formation of covalent bonds in the chain elongation step.

  6. Communications

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Concept
    7. Communications
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    1. Metal–Radical Complexes

      Platinum(II) Complexes with Non-Innocent Ligands: Solid-Phase Synthesis, Redox Chemistry and Luminescence (pages 9482–9486)

      Katja Heinze and Sven Reinhardt

      Article first published online: 24 SEP 2008 | DOI: 10.1002/chem.200801288

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      Innocent or guilty? Catecholato–platinum(II) complexes with phenol-substituted α-diimine ligands are oxidised to the corresponding paramagnetic radical cationic complexes, as well as deprotonated to the corresponding base (see scheme). The radical cations are ortho-benzosemiquinoid in character (EPR spectroscopy). The diamagnetic anions can be described by para-iminoquinonoid resonance formulae and are luminescent at room temperature in fluid solution (static and time-resolved emission).

    2. Dynamic Combinatorial Chemistry

      Selective Extraction of G-Quadruplex Ligands from a Rationally Designed Scaffold-Based Dynamic Combinatorial Library (pages 9487–9490)

      Mads Corvinius Nielsen and Trond Ulven

      Article first published online: 12 SEP 2008 | DOI: 10.1002/chem.200801109

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      Fishing for ligands: The power of dynamic combinatorial chemistry in drug discovery is boosted by a design principle allowing multiple scaffold substituents. Library analysis is furthermore assisted by taking advantage of the UV/Vis spectra of the scaffolds, and an active compound is extracted from the mixture with high selectivity over less active compounds (see figure).

    3. Catalytic Nitrile Reduction

      A General and Environmentally Benign Catalytic Reduction of Nitriles to Primary Amines (pages 9491–9494)

      Stephan Enthaler, Daniele Addis, Kathrin Junge, Giulia Erre and Matthias Beller

      Article first published online: 24 SEP 2008 | DOI: 10.1002/chem.200801600

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      Primary function: The ruthenium-catalyzed hydrogenation of nitriles to give primary amines has been examined in detail with 18 different aromatic and aliphatic nitriles. Superior performance was achieved by using an in situ catalyst, [Ru(cod)methylallyl2] (cod=1,5-cyclooctadiene) and DPPF (see scheme).

    4. Cyclization Reactions

      New Synthetic Approach for the Construction of Multisubstituted 2-Acyl Furans by the IBX-Mediated Cascade Oxidation/Cyclization of cis-2-En-4-yn-1-ols (IBX=2-Iodoxybenzoic Acid) (pages 9495–9498)

      Xiangwei Du, Haoyi Chen and Yuanhong Liu

      Article first published online: 22 SEP 2008 | DOI: 10.1002/chem.200801561

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      Cascading reactions: A new synthetic approach for the construction of multisubstituted 2-acyl furans with high diversity through IBX-mediated (IBX=2-iodoxybenzoic acid) cascade oxidation/cyclization of cis-2-en-4-yn-1-ols in dimethyl sulfoxide has been developed (see scheme). A mechanistic proposal involving IBX-promoted 5-exo-dig cyclization of an enynone intermediate is presented.

    5. Ferrocenyl Ligands

      Mastering the Third Dimension of Salicylaldimine-Type Ligand Systems: Development of a Convenient Route to Bis(“ferrocene–saliminato”)zirconium Chemistry (pages 9499–9502)

      Jochen Niemeyer, Gerald Kehr, Roland Fröhlich and Gerhard Erker

      Article first published online: 11 SEP 2008 | DOI: 10.1002/chem.200801221

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      New family member: The “ferrocene–salimine” system depicted is a chiral three-dimensional relative of the ubiquitous salicyldaldimine ligand family. A short synthesis of the Sp enantiomer and its use in bis(“ferrocene–saliminato”)ZrCl2 chemistry is reported.

    6. Nucleophilic Addition

      Cobalt-Catalyzed Regioselective Synthesis of Indenamine from o-Iodobenzaldimine and Alkyne: Intriguing Difference to the Nickel-Catalyzed Reaction (pages 9503–9506)

      Chuan-Che Liu, Rajendra Prasad Korivi and Chien-Hong Cheng

      Article first published online: 22 SEP 2008 | DOI: 10.1002/chem.200801457

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      Cobalt with a difference: In contrast to nickel- and palladium-catalyzed reactions, the cobalt-catalyzed reaction gave indenamine derivatives instead of isoquinoline derivatives. The difference of the regiochemistry and product formation with respect to the nickel-catalyzed reaction was explained. The indenamines are readily converted to the corresponding indenimines in the presence of tetrabutylammonium fluoride and can then be hydrolyzed to indenones (see scheme).

    7. Zeolites

      Synthesis of Nanocrystalline MFI-Zeolites with Intracrystal Mesopores and Their Application in Fine Chemical Synthesis Involving Large Molecules (pages 9507–9511)

      Rajendra Srivastava, Nobuhiro Iwasa, Shin-ichiro Fujita and Masahiko Arai

      Article first published online: 12 SEP 2008 | DOI: 10.1002/chem.200801113

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      Under control: The synthesis of a MFI-zeolite was effectively controlled and the zeolite length was minimized to 20 nm by adding alkyltriethoxysilane to the conventional hydrothermal synthesis. Owing to intracrystal mesopores and a large external surface area, the zeolite materials (see figure for examples) exhibited a remarkably enhanced catalytic activity for reactions involving large organic molecules, as compared to conventional MFI-zeolites.

    8. Cluster Chemistry

      A New Class of Hydroxo-Bridged Heptacopper(II) Clusters with an Acentrosymmetric Corner-Sharing Double-Cubane Framework Supported by D-Penicillaminedisulfides (pages 9512–9515)

      Asako Igashira-Kamiyama, Junji Fujioka, Seiichi Mitsunaga, Motohiro Nakano, Tatsuya Kawamoto and Takumi Konno

      Article first published online: 22 SEP 2008 | DOI: 10.1002/chem.200801299

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      Copper cubes: An oxygen-bridged heptacopper(II) structure, [Cu73-OH)63-X)2(D-pends)3], bearing D-penicillaminedisulfide (D-H2pends) as an auxiliary ligand was synthesized (see figure). This structure has a novel corner-sharing double-cubane framework without an intramolecular inversion center (i), which exhibits different magnetic behavior to that found in related double-cubane heptacopper(II) clusters with i.

  7. Full Papers

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

      A Phosphotyrosine-Imprinted Polymer Receptor for the Recognition of Tyrosine Phosphorylated Peptides (pages 9516–9529)

      Marco Emgenbroich, Cristiana Borrelli, Sudhirkumar Shinde, Issam Lazraq, Filipe Vilela, Andrew J. Hall, Joakim Oxelbark, Ersilia De Lorenzi, Julien Courtois, Anna Simanova, Jeroen Verhage, Knut Irgum, Kal Karim and Börje Sellergren

      Article first published online: 10 OCT 2008 | DOI: 10.1002/chem.200801046

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      A useful marker: An epitope-imprinting strategy leads to a synthetic phosphotyrosine-selective imprinted polymer receptor. Urea-mediated imprinting of N,O-protected phosphotyrosine (see picture) leads to a synthetic receptor capable of selectively extracting phosphotyrosine peptides in the presence of phosphoserine, phosphothreonine, and non-phosphorylated peptides.

    2. Fluorophosphorylation

      Stereoselective Glycal Fluorophosphorylation: Synthesis of ADP-2-fluoroheptose, an Inhibitor of the LPS Biosynthesis (pages 9530–9539)

      Hirofumi Dohi, Régis Périon, Maxime Durka, Michael Bosco, Yvain Roué, François Moreau, Sylvestre Grizot, Arnaud Ducruix, Sonia Escaich and Stéphane P. Vincent

      Article first published online: 2 OCT 2008 | DOI: 10.1002/chem.200801279

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      Antibacterial agent 00F: Heptosides are found in important bacterial glycolipids such as lipopolysaccharide (LPS), the biosynthesis of which is targeted for the development of novel antibacterial agents. This work describes the synthesis of a fluorinated analog of ADP-L-glycero-β-D-manno-heptopyranose, the donor substrate of the heptosyl transferase WaaC, which catalyzes the incorporation of this carbohydrate into LPS (see scheme).

    3. Cubanes

      Structure, Magnetic Properties, Polarized Neutron Diffraction, and Theoretical Study of a Copper(II) Cubane (pages 9540–9548)

      Christophe Aronica, Yurii Chumakov, Erwann Jeanneau, Dominique Luneau, Petr Neugebauer, Anne-Laure Barra, Béatrice Gillon, Antoine Goujon, Alain Cousson, Javier Tercero and Eliseo Ruiz

      Article first published online: 12 SEP 2008 | DOI: 10.1002/chem.200800557

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      Cubane copper: Syntheses, X-ray and neutron diffraction crystal structures, magnetic properties, high-field–high-frequency EPR (HF-EPR), spin density, and theoretical description of a tetranuclear CuII complex (see figure) with a cubane-like structure are presented.

    4. Autoxidation

      Mechanisms of Air Oxidation of Ethoxylated Surfactants—Computational Estimations of Energies and Reaction Behaviors (pages 9549–9554)

      Carina Bäcktorp, Anna Börje, J. Lars G. Nilsson, Ann-Therese Karlberg, Per-Ola Norrby and Gunnar Nyman

      Article first published online: 11 SEP 2008 | DOI: 10.1002/chem.200800545

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      Autoxidation mechanism: The mechanism of autoxidation of ethoxylated surfactants has been investigated by DFT methods. In addition to the standard radical-chain mechanism, intermediate hydroxyl radicals can undergo intramolecular fragmentation reactions, as exemplified here.

    5. Lanthanide Clusters

      Elusive Trimethyllanthanum: Snapshots of Extensive Methyl Group Degradation in La[BOND]Al Heterobimetallic Complexes (pages 9555–9564)

      Laura C. H. Gerber, Erwan Le Roux, Karl W. Törnroos and Reiner Anwander

      Article first published online: 11 SEP 2008 | DOI: 10.1002/chem.200801174

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      Metal-promoted C1cannibalism: Separation of Me3Al(PMe3) occurs slowly when [La(AlMe4)3] reacts with trimethylphosphine and prolonged reaction periods lead to multiple C[BOND]H bond activation as evidenced by the isolation of two distinct cuboid La4Al8 clusters and an La5Al9 cluster (see figure) bearing methylene, methine, and carbide units.

    6. Coordination Polymers

      Zipped-Up Chain-Type Coordination Polymers: Unsymmetrical Amide-Containing Ligands Inducing β-Sheet or Helical Structures (pages 9565–9576)

      Kazuhiro Uemura, Yuki Kumamoto and Susumu Kitagawa

      Article first published online: 9 SEP 2008 | DOI: 10.1002/chem.200800806

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      Charming chains: Crystal structures of one-dimensional AgI coordination polymers involving py-CONH-(CH2)n-py (py=pyridine; n=0, 1) derivatives were determined by single-crystal X-ray analyses; they showed biomimetic β-sheet and helical structural motifs (see picture).

    7. Self-Assembly

      Self-Assembly of Oligo(para-phenylenevinylene)s through Arene—Perfluoroarene Interactions: π Gels with Longitudinally Controlled Fiber Growth and Supramolecular Exciplex-Mediated Enhanced Emission (pages 9577–9584)

      Sukumaran S. Babu, Vakayil K. Praveen, Seelam Prasanthkumar and Ayyappanpillai Ajayaghosh

      Article first published online: 9 SEP 2008 | DOI: 10.1002/chem.200801255

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      All under control: The arene—perfluoroarene (ArH–ArF) interaction is found to be efficient for the self-assembly of oligo(para-phenylenevinylene)s (OPVs) in solution with controlled longitudinal fiber growth that leads to gelation (see picture). The fluorescence quenching that commonly occurs during the self-assembly of OPVs could be prevented by exciplex formation with N,N-dimethylaniline, which occurs only in the gel state.

    8. Fullerenes

      Chlorinated Derivatives of C78-Fullerene Isomers with Unusually Short Intermolecular Halogen–Halogen Contacts (pages 9585–9590)

      Kalin S. Simeonov, Konstantin Yu. Amsharov and Martin Jansen

      Article first published online: 12 SEP 2008 | DOI: 10.1002/chem.200801182

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      Three chlorinated derivatives of the isomers C78(2), C78(3), and C78(4) were synthesized by highly selective chlorination in a TiCl4/Br2 mixture (see scheme). Detailed analysis of the crystal structures of the three fullerene derivatives, C78(2)Cl18, C78(3)Cl18, and C78(4)Cl18, has revealed the presence of unusual, short intermolecular halogen–halogen contacts, the nature of which is discussed.

    9. Enzymatic Mechanisms

      Glutathione Transferase: New Model for Glutathione Activation (pages 9591–9598)

      Daniel F. A. R. Dourado, Pedro Alexandrino Fernandes, Bengt Mannervik and Maria João Ramos

      Article first published online: 12 SEP 2008 | DOI: 10.1002/chem.200800946

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      Bridging the gap: It is proposed that, after an initial conformational rearrangement of glutathione (GSH), a water molecule, acting as a bridge, is able to transfer the proton from the GSH thiol group to the GSH glutamyl α-carboxylate group (see models).

    10. Receptors

      Structure–Activity Relationships in Cholapod Anion Carriers: Enhanced Transmembrane Chloride Transport through Substituent Tuning (pages 9599–9606)

      Beth A. McNally, Atanas V. Koulov, Timothy N. Lambert, Bradley D. Smith, Jean-Baptiste Joos, Adam L. Sisson, John P. Clare, Valentina Sgarlata, Luke W. Judd, Germinal Magro and Anthony P. Davis

      Article first published online: 4 SEP 2008 | DOI: 10.1002/chem.200801163

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      Optimised anion carriers: A study of 16 steroid-based anion transporters shows that changing substituents can have dramatic effects on transport rates. The current champion (see diagram) is effective in vesicle membranes with a transporter/lipid ratio of 1:250 000 (<2 transporter molecules per vesicle in the system studied).

    11. Computational Chemistry

      Origin of Diastereocontrol in the Oxy-Michael Reactions of δ-Lactol Anions: A Computational and Experimental Study (pages 9607–9612)

      Robert D. Richardson, Felix A. Hernandez-Juan, John W. Ward and Darren J. Dixon

      Article first published online: 26 SEP 2008 | DOI: 10.1002/chem.200801368

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      Controlling the lactols: DFT, ab initio and experimental techniques have been used to probe the stereocontrol in the alkylation and oxy-Michael reactions of substituted δ-lactols (see scheme).

    12. Donor–Acceptor Systems

      Phosphorescent Thymidine Triphosphate Sensor Based on a Donor–Acceptor Ensemble System using Intermolecular Energy Transfer (pages 9613–9619)

      Tae-Hyuk Kwon, Hee Jin Kim and Jong-In Hong

      Article first published online: 18 SEP 2008 | DOI: 10.1002/chem.200801260

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      Take your pick! An ensemble system consisting of an energy acceptor (2) and an energy donor (1) exhibited selective luminescence enhancement upon binding to thymidine 5′-triphosphate (TTP) over other nucleotides in HEPES buffer.

    13. Sultone Reactivity

      Reactivity of the 4-Amino-5H-1,2-Oxathiole-2,2-Dioxide Heterocyclic System: A Combined Experimental and Theoretical Study (pages 9620–9632)

      Sonia de Castro, M. Teresa Peromingo, Angel E. Lozano, María-José Camarasa and Sonsoles Velázquez

      Article first published online: 9 SEP 2008 | DOI: 10.1002/chem.200800433

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      Conformational changes count: The reactivity of the β-amino-γ-sultone system, with spiranic or non-spiranic substituents on C-5, is described. Theoretical and experimental studies show that the interaction of a base on the C-4 position of the spiranic systems induces a conformational change that breaks the planarity of the sultone ring, increasing the reactivity of the C-3 and N-4 positions towards electrophiles (see scheme).

    14. Sensors

      A New Route to the Considerable Enhancement of Glucose Oxidase (GOx) Activity: The Simple Assembly of a Complex from CdTe Quantum Dots and GOx, and Its Glucose Sensing (pages 9633–9640)

      Lihua Cao, Jian Ye, Lili Tong and Bo Tang

      Article first published online: 15 SEP 2008 | DOI: 10.1002/chem.200800681

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      Glucose nanosensor: A complex made from CdTe quantum dots (QDs) and glucose oxidase (GOx) has been facilely assembled to achieve enhanced enzymatic activity and a wide active temperature range of GOx. The principle is based on the fluorescence quenching of CdTe QDs and a cyclic electron-transfer mechanism (see scheme).

    15. Flow Synthesis

      Gold-Film-Catalysed Hydrosilylation of Alkynes by Microwave-Assisted, Continuous-Flow Organic Synthesis (MACOS) (pages 9641–9646)

      Gjergji Shore and Michael G. Organ

      Article first published online: 24 SEP 2008 | DOI: 10.1002/chem.200801610

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      Thin gold films have been deposited on the inside of glass capillaries through which silanes and terminal alkynes are flowed (see scheme). Under microwave irradiation, hydrosilylation occurs very rapidly leading to the synthesis of vinylsilanes in very high chemical conversions. The films are reuseable and no leaching of gold nanoparticles into the eluent stream was observed (lower level of detection: δ=50 ppm).

    16. NMR Spectroscopy

      Contributions from Atomic p(Se), d(Se), and f(Se) Orbitals to Absolute Paramagnetic Shielding Tensors in Neutral and Charged SeHn and Some Oxides Including the Effect of Methyl and Halogen Substitutions on σp(Se) (pages 9647–9655)

      Waro Nakanishi, Satoko Hayashi, Kenji Narahara and Masahiko Hada

      Article first published online: 22 SEP 2008 | DOI: 10.1002/chem.200800844

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      Chemical shift prediction: Contributions from atomic p(Se), d(Se), and f(Se) are evaluated for various selenium compounds. The contributions from p(Se) are >96 % for Se*Hn (*=null, +, or −: n ≤ 3) and SeH4 (Td). The Me and X substitutions increase the p(Se) contributions. Consequently, σp(Se) can be substantially analyzed based on p(Se), especially by 4p(Se), for most of Se compounds.

    17. Organic Synthesis

      Highly Stereoselective Iodolactonization of 4,5-Allenoic Acids—An Efficient Synthesis of 5-(1′-Iodo-1′(Z)-alkenyl)-4,5-dihydro-2(3H)-furanones (pages 9656–9664)

      Xinpeng Jiang, Chunling Fu and Shengming Ma

      Article first published online: 9 SEP 2008 | DOI: 10.1002/chem.200801363

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      An efficient and highly stereoselective synthesis of optically active γ-butyrolactones through the iodolactonization of 4,5-allenoic acid was observed (see scheme). The reaction of axially optically active 4,5-allenoic acids with N-iodosuccinimide (NIS) afforded the corresponding products without loss of chirality, whereas the substrates with a center of chirality at the 3-position reacted with I2 to give the optically active trans-4,5-disubstituted γ-butyrolactones.

    18. Film Patterning

      Interfacial Behavior and Film Patterning of Redox-Active Cationic Copper(II)-Containing Surfactants (pages 9665–9674)

      Jeffery A. Driscoll, Marco M. Allard, Libo Wu, Mary Jane Heeg, Sandro R. P. da Rocha and Cláudio N. Verani

      Article first published online: 12 SEP 2008 | DOI: 10.1002/chem.200801215

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      Film star: The synthesis, characterization, electrochemical and amphiphilic properties, and the patterning of Langmuir films of a series of single-tail amphiphiles and their copper(II)-containing complexes is discussed (see figure).

    19. Electrophilicity

      Determination of the Electrophilicity Parameters of Diethyl Benzylidenemalonates in Dimethyl Sulfoxide: Reference Electrophiles for Characterizing Strong Nucleophiles (pages 9675–9682)

      Oliver Kaumanns, Roland Lucius and Herbert Mayr

      Article first published online: 12 SEP 2008 | DOI: 10.1002/chem.200801277

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      Extending the electrophilicity scale: Benzylidenemalonates are considerably less electrophilic than benzylidene Meldrum's acids, and allow us to extend the series of reference electrophiles (see graphic) used for the construction of nucleophilicity scales by six orders of magnitude on the low-reactivity end.

    20. Receptors

      Metal-Controlled Anion-Binding Tendencies of the Thiourea Unit of Thiosemicarbazones (pages 9683–9696)

      Valeria Amendola, Massimo Boiocchi, Luigi Fabbrizzi and Lorenzo Mosca

      Article first published online: 12 SEP 2008 | DOI: 10.1002/chem.200800801

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      Too acidic anion receptor! 1:2 FeII and NiII complexes of thiosemicarbazones expose their thiourea subunits to the outside (see figure). They are prone to donate bifurcate H-bonds to anions. However, the metal centre exerts such a strong polarizing effect that most anions (e.g., CH3COO, NO2, F) induce deprotonation of one N-H fragment of each thiosemicarbazone ligand.

    21. Reaction mechanism

      Solvent-Dependent Changes in the Triazolinedione–Alkene Ene Reaction Mechanism (pages 9697–9705)

      Georgios C. Vougioukalakis, Manolis M. Roubelakis, Mariza N. Alberti and Michael Orfanopoulos

      Article first published online: 24 SEP 2008 | DOI: 10.1002/chem.200800920

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      The mechanism of the ene reaction of triazolinedione (RTAD) with simple alkenes depends on solvent polarity (see scheme). In aprotic solvents, a tight aziridinium imide intermediate with insignificant equilibration to its open intermediate is suggested. In protic solvents, large, non-stereochemically-dependent kinetic isotope effects suggest a loose aziridinium imide intermediate that equilibrates extensively with its open intermediate and the starting reagents.

    22. Organic Chemistry

      Synthesis of Substituted Phenols by Using the Ring-Closing Metathesis/Isoaromatization Approach (pages 9706–9713)

      Kazuhiro Yoshida, Rintaro Narui and Tsuneo Imamoto

      Article first published online: 9 SEP 2008 | DOI: 10.1002/chem.200800943

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      Aromatic synthesis: Ring-closing olefin metathesis (RCM) of 4-methylene-1,7-octadien-3-ones 1, followed by isomerization of the carbon[BOND]carbon double bond of 6-methylene-2-cyclohexenones 2 from exo to endo, produced various phenols 3. As an application of the method, the RCM/Mizoroki–Heck reaction of 1 was proven to be also effective for the synthesis of phenols having an additional substituent at ortho-benzylic position.

    23. Reaction Mechanisms

      Aromatic Hydroxylation in a Copper Bis(imine) Complex Mediated by a μ-η22 Peroxo Dicopper Core: A Mechanistic Scenario (pages 9714–9729)

      Ole Sander, Anja Henß, Christian Näther, Christian Würtele, Max C. Holthausen, Siegfried Schindler and Felix Tuczek

      Article first published online: 11 SEP 2008 | DOI: 10.1002/chem.200800799

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      Art of attack: Aromatic ligand hydroxylation that occurs on reaction of a dicopper bis(imine) complex with O2 was studied spectroscopically and kinetically, and the energetics of the hydroxylation pathway were determined theoretically. Calculations show that not the equation imageorbital of the μ-η22-peroxo intermediate is involved in electrophilic attack on the arene ring of the ligand, which is the major barrier on the reaction pathway, but the σ* orbital, as depicted schematically.

    24. Nanorods

      Nucleation and Growth of BaFxCl2−x Nanorods (pages 9730–9735)

      Ting Xie, Shuai Li, Wenbei Wang, Qing Peng and Yadong Li

      Article first published online: 9 SEP 2008 | DOI: 10.1002/chem.200800363

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      Spare the rod! A mechanism for the nucleation and growth of nanocrystals (see graphic) was put forward, in view of the surface chemical thermodynamics, to explain the experimental results, which showed that the specific surface area increased as the initial concentrations were multiplied.

    25. Platinum Complexes

      Structures and Solvatochromic Phosphorescence of Dicationic Terpyridyl–Platinum(II) Complexes with Foldable Oligo(ortho-phenyleneethynylene) Bridging Ligands (pages 9736–9746)

      Ming-Xin Zhu, Wei Lu, Nianyong Zhu and Chi-Ming Che

      Article first published online: 24 SEP 2008 | DOI: 10.1002/chem.200800394

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      Things that glow red in water: The uniquely red-shifted and enhanced phosphorescence from the dicationic terpyridyl–PtII complexes with foldable ortho-PE(n) bridges (PE=phenyleneethynylene) in aerated H2O/CH3CN solvent mixtures was tentatively attributed to the molecular aggregation and intramolecular hydrophobic folding of the ortho-PE(n) (n≥3) moieties (see figure).

    26. Dialuminum Compounds

      Aluminum Compounds Containing η1- and/or η5-Bidentate Dianionic Pyrrolyl–Methylamide Ligands (pages 9747–9753)

      Ya-Chi Chen, Che-Yu Lin, Chun-Yin Li, Jui-Hsien Huang, Ling-Chueh Chang and Ting-Yu Lee

      Article first published online: 12 SEP 2008 | DOI: 10.1002/chem.200800679

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      Fine tuning aluminum: A good synthetic route has been found for a series of dialuminum compounds (see figure) containing dianionic substituted pyrrolyl ligands. These compounds were used successfully as catalysts for the ring-opening polymerization of ε-caprolactone.

    27. Fluorescent Chemosensors

      Catechol Derivatives as Fluorescent Chemosensors for Wide-Range pH Detection (pages 9754–9763)

      Emilia Evangelio, Jordi Hernando, Inhar Imaz, Gisela G. Bardají, Ramon Alibés, Félix Busqué and Daniel Ruiz-Molina

      Article first published online: 11 SEP 2008 | DOI: 10.1002/chem.200800722

      Thumbnail image of graphical abstract

      On again, off again: A new catechol-based derivative with complementary “off–on–off” and “on–off–on” emission profiles upon pH variation has been shown to exhibit excellent acidity detection over a broad pH range by applying a dual-wavelength detection methodology (see picture).

    28. Gold Nanorods

      Well-Controlled Synthesis of Au@Pt Nanostructures by Gold-Nanorod-Seeded Growth (pages 9764–9771)

      Lili Feng, Xiaochun Wu, Lirong Ren, Yanjuan Xiang, Weiwei He, Ke Zhang, Weiya Zhou and Sishen Xie

      Article first published online: 4 SEP 2008 | DOI: 10.1002/chem.200800544

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      Au@Pt nanostructures for SPR-based sensing: Pt nanodots were formed on Au nanorods (see graphic) using a simple seed-mediated growth method. The Au@Pt nanostructure exhibited an evident longitudinal surface plasmon resonance (SPR) in the near-infrared region, thus opening the potential of using these nanostructures for SPR-based sensing.

    29. Ruthenium Chemistry

      Recent Advances in “Formal” Ruthenium-Catalyzed [2+2+2] Cycloaddition Reactions of Diynes to Alkenes (pages 9772–9778)

      Silvia García-Rubín, Jesús A. Varela, Luis Castedo and Carlos Saá

      Article first published online: 2 SEP 2008 | DOI: 10.1002/chem.200801088

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      A formal event in chemistry! “Formal” RuII-catalyzed [2+2+2] cycloaddition reactions of 1,6-diynes and alkenes were found to give bicyclic 1,3-cyclohexadienes (see scheme). The regio- and stereochemical course of the reaction depends on the substitution of the 1,6-diyne.

    30. Electrochemical Sensors

      Carbon-Nanotube–Alginate Composite Modified Electrode Fabricated by In Situ Gelation for Capillary Electrophoresis (pages 9779–9785)

      Bangguo Wei, Joseph Wang, Zhi Chen and Gang Chen

      Article first published online: 4 SEP 2008 | DOI: 10.1002/chem.200801124

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      Sensitive detector: A novel carbon-nanotube (CNT)–alginate composite modified electrode was developed as a sensitive amperometric detector for capillary electrophoresis. The performance of this system was demonstrated by the separation and detection of five caffeic acid derivatives. The surface morphology of the CNT–alginate composites on an electrode is shown in the SEM image.

    31. Nanomaterials

      Tetraethylenepentamine-Directed Controllable Synthesis of Wurtzite ZnSe Nanostructures with Tunable Morphology (pages 9786–9791)

      Baojuan Xi, Shenglin Xiong, Dechen Xu, Jingfa Li, Hongyang Zhou, Jun Pan, Jiangying Li and Yitai Qian

      Article first published online: 12 SEP 2008 | DOI: 10.1002/chem.200801041

      Thumbnail image of graphical abstract

      Pick'n'mix ZnSe nanostructures: Various wurtzite ZnSe architectural structures (see figure) have been successfully prepared through a novel tetraethylenepentamine-directed method in a ternary solution by adjusting the reaction parameters. This is the first preparation of complex hollow structures of ZnSe crystals with hierarchy through a simple solution-based route.

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      Preview: Chem. Eur. J. 32/2008 (page 9795)

      Article first published online: 21 OCT 2008 | DOI: 10.1002/chem.200890127

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