Chemistry - A European Journal

Cover image for Vol. 17 Issue 51

December 16, 2011

Volume 17, Issue 51

Pages 14305–14691

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Communications
    9. Full Papers
    10. Preview
    1. Cover Picture: A Diverted Total Synthesis of Mycolactone Analogues: An Insight into Buruli Ulcer Toxins (Chem. Eur. J. 51/2011) (page 14305)

      Anne-Caroline Chany, Dr. Virginie Casarotto, Dr. Marjorie Schmitt, Prof. Dr. Céline Tarnus, Dr. Laure Guenin-Macé, Dr. Caroline Demangel, Dr. Olivier Mirguet, Prof. Dr. Jacques Eustache and Dr. Nicolas Blanchard

      Article first published online: 14 DEC 2011 | DOI: 10.1002/chem.201190260

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      150 Years after the first description of Buruli ulcer, a devastating mycobacterial infection, a diverted total synthesis (DTS) approach of mycolactone analogues has been developed, relying on metal-mediated and metal-catalyzed transformations. These DTS efforts have provided relevant insights into structure–activity relationships based on cytopathic assays on L929 fibroblasts. The lowest concentration inducing a cytopathic effect was determined for selected analogues, allowing a clear picture to emerge by comparison with the natural toxins. For more details, see the Full Paper by N. Blanchard et al. on page 14413 ff. Cover art by David Vandergucht.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Communications
    9. Full Papers
    10. Preview
    1. Inside Cover: Construction of 1D π-Stacked Superstructures with Inclusion Channels through Symmetry-Decreasing Crystallization of Discotic Molecules of C3 Symmetry (Chem. Eur. J. 51/2011) (page 14306)

      Dr. Ichiro Hisaki, Hirofumi Senga, Hajime Shigemitsu, Dr. Norimitsu Tohnai and Prof. Dr. Mikiji Miyata

      Article first published online: 14 DEC 2011 | DOI: 10.1002/chem.201190261

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      A 1D, π-stacked, columnar assembly composed of discotic π-conjugated molecules is one of the key architectures for organic semiconductor materials. In their Communication on page 14348 ff., I. Hisaki, M. Miyata et al. demonstrate that a supramolecular architecture with both 1D π-stacked columns and inclusion channels can be constructed through symmetry-decreasing crystallization by using a dehydrobenzo[12]annulene derivative with C3 symmetry. The structure experiences spontaneous guest desorption under ambient conditions; this results in shrinkage of the crystallographic cell.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Communications
    9. Full Papers
    10. Preview
    1. Graphical Abstract: Chem. Eur. J. 51/2011 (pages 14309–14319)

      Article first published online: 14 DEC 2011 | DOI: 10.1002/chem.201190262

  4. Corrigendum

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Communications
    9. Full Papers
    10. Preview
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      Corrigendum: Systematic Synthesis of Inhibitors of the Two First Enzymes of the Bacterial Heptose Biosynthetic Pathway: Towards Antivirulence Molecules Targeting Lipopolysaccharide Biosynthesis (page 14319)

      Dr. Maxime Durka, Dr. Abdellatif Tikad, Dr. Régis Périon, Dr. Michael Bosco, Dr. Mounir Andaloussi, Stéphanie Floquet, Elodie Malacain, Dr. François Moreau, Dr. Mayalen Oxoby, Dr. Vincent Gerusz and Prof. Stéphane P. Vincent

      Article first published online: 14 DEC 2011 | DOI: 10.1002/chem.201103709

  5. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Communications
    9. Full Papers
    10. Preview
  6. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Communications
    9. Full Papers
    10. Preview
    1. Lithium-Ion Batteries

      Lithium-Ion Conducting Electrolyte Salts for Lithium Batteries (pages 14326–14346)

      Dr. Vanchiappan Aravindan, Dr. Joe Gnanaraj, Prof. Srinivasan Madhavi and Prof. Hua-Kun Liu

      Article first published online: 24 NOV 2011 | DOI: 10.1002/chem.201101486

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      All charged up: An overview of the various types of lithium salts used to conduct Li+ ions in electrolyte solutions for rechargeable lithium batteries is presented. Emphasis is paid towards lithium salts and their ionic conductivity in conventional solutions, solid electrolyte interface formation towards carbonaceous anodes and the effect of the anion on the aluminium current collector.

  7. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Communications
    9. Full Papers
    10. Preview
    1. Crystallization

      Construction of 1D π-Stacked Superstructures with Inclusion Channels through Symmetry-Decreasing Crystallization of Discotic Molecules of C3 Symmetry (pages 14348–14353)

      Dr. Ichiro Hisaki, Hirofumi Senga, Hajime Shigemitsu, Dr. Norimitsu Tohnai and Prof. Dr. Mikiji Miyata

      Article first published online: 23 NOV 2011 | DOI: 10.1002/chem.201103133

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      Supramolecular architectures that possess both 1D π-stacked columns and inclusion channels were constructed by symmetry-decreasing crystallization of dehydrobenzo[12]annulene (DBA) derivatives with naphthyl arms and C3 symmetry (see figure). The crystallization can be interpreted as i) formation of a two-fold column, ii) layer formation, and iii) lamination of the layer accompanied by guest inclusion.

    2. Supramolecular Engineering

      Supramolecular Engineering through Temperature-Induced Chemical Modification of 2H-Tetraphenylporphyrin on Ag(111): Flat Phenyl Conformation and Possible Dehydrogenation Reactions (pages 14354–14359)

      Dr. Giovanni Di Santo, Dr. Stephan Blankenburg, Dr. Carla Castellarin-Cudia, Dr. Mattia Fanetti, Dr. Patrizia Borghetti, Prof. Luigi Sangaletti, Dr. Luca Floreano, Dr. Alberto Verdini, Dr. Elena Magnano, Dr. Federica Bondino, Dr. Carlo A. Pignedoli, Dr. Manh-Thuong Nguyen, Dr. Roberto Gaspari, Dr. Daniele Passerone and Dr. Andrea Goldoni

      Article first published online: 23 NOV 2011 | DOI: 10.1002/chem.201102268

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      Scratching the surface: Formation of a monolayer of 2H-tetraphenylporphyrins (2H-TPP) on Ag(111), either by sublimation of a multilayer in the range 525–600 K or by annealing (at the same temperature) a monolayer deposited at room temperature, induces a chemical modification of the molecules (see figure). Rotation of the phenyl rings into a flat conformation is observed and tentatively explained, by using DFT calculations, as a peculiar reaction due to molecular dehydrogenation.

    3. Zeolites

      Synthesis of Dicationic Ionic Liquids and their Application in the Preparation of Hierarchical Zeolite Beta (pages 14360–14365)

      Rajkumar Kore, Dr. Biswarup Satpati and Dr. Rajendra Srivastava

      Article first published online: 23 NOV 2011 | DOI: 10.1002/chem.201102946

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      Piperidine- and imidazole-based dicatoinic ionic liquids have been developed for the synthesis of zeolite Beta. Hierarchical Beta has a larger surface area and pore volume than conventional Beta. Beta derived from a dicationic ionic liquid exhibited remarkably higher catalytic activity than the conventional Beta. Experimental evidence and DFT calculations suggest that only a suitable conformation of such dicationic ionic liquids is able to form zeolite Beta (see scheme).

    4. Palladium Catalysis

      Palladium-Catalyzed Cascade Cyclization of Ynamides to Azabicycles (pages 14366–14370)

      Rebecca L. Greenaway, Dr. Craig D. Campbell, Oliver T. Holton, Dr. C. Adam Russell and Dr. Edward A. Anderson

      Article first published online: 24 NOV 2011 | DOI: 10.1002/chem.201102880

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      Cascade reactions: A modular assembly of azabicycles by using a cascade cyclization/Suzuki coupling/6π-electrocyclization of bromoenynamides is reported (see scheme). The reaction offers a wide substituent scope on the bicyclic aminodiene products, which can be selectively oxidized as a general approach to aromatic azabicycles.

    5. C[BOND]H Activation

      Silanol as a Removable Directing Group for the PdII-Catalyzed Direct Olefination of Arenes (pages 14371–14374)

      Dr. Cong Wang and Prof. Dr. Haibo Ge

      Article first published online: 17 NOV 2011 | DOI: 10.1002/chem.201103171

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      Need some direction? Silanol was developed as a directing group for the PdII-catalyzed oxidative Heck-type reaction of arenes. A one-pot C[BOND]H activation/desilylation process of benzyldiisopropylsilanol was also demonstrated, providing a powerful approach for the synthesis of ortho-alkenyl-substituted alkylarenes (see scheme). Considering the easily attachable and readily removable properties of the silanol group, this reaction will find broad synthetic applications.

    6. Hydrogen Transfer

      A Convenient and General Ruthenium-Catalyzed Transfer Hydrogenation of Nitro- and Azobenzenes (pages 14375–14379)

      Dr. Rajenahally V. Jagadeesh, Gerrit Wienhöfer, Felix A. Westerhaus, Dr. Annette-Enrica Surkus, Dr. Henrik Junge, Dr. Kathrin Junge and Prof. Dr. Matthias Beller

      Article first published online: 23 NOV 2011 | DOI: 10.1002/chem.201102276

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      An easily accessible in situ catalyst composed of [{RuCl2(p-cymene)}2] and terpyridine has been developed for the selective transfer hydrogenation of aromatic nitro and azo compounds. The procedure is general and the selectivity of the catalyst has been demonstrated by applying a series of structurally diverse nitro and azo compounds (see scheme).

    7. Asymmetric Synthesis

      Asymmetric Synthesis of β-Adrenergic Blockers through Multistep One-Pot Transformations Involving In Situ Chiral Organocatalyst Formation (pages 14380–14384)

      Dr. Shengwei Wei, Regina Messerer and Prof. Dr. Svetlana B. Tsogoeva

      Article first published online: 23 NOV 2011 | DOI: 10.1002/chem.201102931

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      Two birds one stone: A new atom-economical one-pot approach to enantioselective chiral drug synthesis, involving in situ multistep organocatalyst formation and the application of the reaction for multistep sequential synthesis of β-adrenergic blockers is disclosed (see scheme).

    8. C[BOND]H Activation

      Catalytic C[BOND]H Bond Activation at Nanoscale Lewis Acidic Aluminium Fluorides: H/D Exchange Reactions at Aromatic and Aliphatic Hydrocarbons (pages 14385–14388)

      Dr. Martin H. G. Prechtl, Dipl.-Chem. Michael Teltewskoi, Dr. Anton Dimitrov, Prof. Dr. Erhard Kemnitz and Prof. Dr. Thomas Braun

      Article first published online: 29 NOV 2011 | DOI: 10.1002/chem.201102853

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      Nanoscopic amorphous Lewis acidic aluminium fluorides, such as aluminium chlorofluoride (ACF) and high-surface aluminium fluoride (HS-AlF3), are capable of activating C[BOND]H bonds of aliphatic hydrocarbons. H/D exchange reactions are catalysed under mild conditions (40 °C).

    9. Cross-Coupling Reactions

      Room-Temperature Palladium-Catalyzed Negishi-Type Coupling: A Combined Experimental and Theoretical Study (pages 14389–14393)

      Philippe Ribagnac, Dr. Matthias Blug, Jose Villa-Uribe, Dr. Xavier-Frédéric Le Goff, Dr. Corinne Gosmini and Dr. Nicolas Mézailles

      Article first published online: 25 NOV 2011 | DOI: 10.1002/chem.201102369

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      An air-stable, bulky electron-accepting phosphine ligand (phosphabarrelene) allows the easy reduction of a PdII precursor to a Pd0 complex, highly active in room-temperature Negishi-type cross-coupling. DFT calculations show that the use of the electron-accepting ligand favors both transmetalation (TM) and reductive-elimination (RE) processes (see scheme; OA=oxidative addition).

    10. Cluster Compounds

      From Molecule to Materials: Crystalline Superlattices of Nanoscopic CdS Clusters (pages 14394–14398)

      Tetyana I. Levchenko, Dr. Christian Kübel, Prof. Yining Huang and Prof. John F. Corrigan

      Article first published online: 18 NOV 2011 | DOI: 10.1002/chem.201102487

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      Make way for a superlattice! A crystalline 3D superlattice of 2.3 nm molecular CdS nanoclusters was prepared from a convenient mononuclear cadmium thiophenolate precursor. HRTEM and STEM tomography show highly crystalline repetition of monodisperse frameworks (see figure). This combined with elemental and thermogravimetric analyses suggests an approximate formula [Cd130S103(SPh)54].

  8. Full Papers

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Review
    8. Communications
    9. Full Papers
    10. Preview
    1. Porphyrinoids

      Synthesis and Properties of Hybrid Porphyrin Tapes (pages 14400–14412)

      Takayuki Tanaka, Byung Sun Lee, Dr. Naoki Aratani, Dr. Min-Chul Yoon, Prof. Dr. Dongho Kim and Prof. Dr. Atsuhiro Osuka

      Article first published online: 25 NOV 2011 | DOI: 10.1002/chem.201102889

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      All taped up! Hybrid porphyrin tapes consisting of a 3,5-di-tert-butylphenyl-substituted donor-type porphyrin and a pentafluorophenyl-substituted acceptor-type porphyrin were prepared and characterized by 1H NMR and UV/Vis absorption spectroscopy, cyclic voltammetry, and X-ray diffraction analysis. The hybrid porphyrin tapes possess improved solubility and stability and exhibit larger two-photon absorption cross-section values with respect to tapes consisting of donor-type porphyrins only.

    2. Total Synthesis

      A Diverted Total Synthesis of Mycolactone Analogues: An Insight into Buruli Ulcer Toxins (pages 14413–14419)

      Anne-Caroline Chany, Dr. Virginie Casarotto, Dr. Marjorie Schmitt, Prof. Dr. Céline Tarnus, Dr. Laure Guenin-Macé, Dr. Caroline Demangel, Dr. Olivier Mirguet, Prof. Dr. Jacques Eustache and Dr. Nicolas Blanchard

      Article first published online: 30 NOV 2011 | DOI: 10.1002/chem.201102542

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      Subtle changes, big impacts! Deciphering the functional interactions of mycolactones is of fundamental importance for the understanding and ultimately the control of Buruli ulcer, a devastating mycobacterial infection. A diverted total-synthesis approach of mycolactone analogues is reported. It provides the first insights into their structure–activity relationship based on cytopathic assays on L929 fibroblasts (see figure).

    3. Molecular Recognition

      Remarkably Selective Recognition of Iodobenzene Derivatives by a Macrocyclic Bis-PtII Metallohost (pages 14420–14428)

      Dr. Robert Trokowski, Dr. Shigehisa Akine and Dr. Tatsuya Nabeshima

      Article first published online: 16 NOV 2011 | DOI: 10.1002/chem.201101650

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      π in the face: The design and synthesis of a self-assembled bis-PtII dimer with quino[8,7-b][1,10]phenanthroline as an extended π-face contact area is described (see figure). It acts as the first artificial receptor with remarkably high affinity toward iodinated aromatic compounds based on noncovalent iodine⋅⋅⋅aromatic-plane interactions in a “side-on” fashion.

    4. Nucleic Acids

      Biophysical and Cellular-Uptake Properties of Mixed-Sequence Pyrrolidine–Amide Oligonucleotide Mimics (pages 14429–14441)

      Dr. Roberta J. Worthington and Prof. Dr. Jason Micklefield

      Article first published online: 11 NOV 2011 | DOI: 10.1002/chem.201101950

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      POM fits: Short pyrrolidine–amide oligonucleotide mimics (POMs) have shown promising DNA/RNA recognition properties. To better understand these characteristics, several mixed-sequence POM oligomers were synthesised. These results show that POMs have the potential for use in a variety of applications, including the targeting of cellular RNAs (see figure), alongside other modified nucleic acids.

    5. Molecular Devices

      Huge Dielectric Response and Molecular Motions in Paddle-Wheel [CuII2(Adamantylcarboxylate)4(DMF)2]⋅(DMF)2 (pages 14442–14449)

      Dr. Qiong Ye, Kiyonori Takahashi, Dr. Norihisa Hoshino, Dr. Takemitsu Kikuchi, Prof. Tomoyuki Akutagawa, Prof. Shin-ichiro Noro, Prof. Sadamu Takeda and Prof. Takayoshi Nakamura

      Article first published online: 18 NOV 2011 | DOI: 10.1002/chem.201101743

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      Cooperative motions: Cooperative dynamic motions of adamantyl groups and DMF molecules were observed in [CuII2(ADCOO)4(DMF)2]⋅(DMF)2, resulting in huge dielectric responses in low-frequency regions (see figure).

    6. Reaction Mechanisms

      Mechanism Selection for Regiocontrol in Base-Assisted, Palladium-Catalysed Direct C[BOND]H Coupling with Halides: First Approach for Oxazole- and Thiazole-4-Carboxylates (pages 14450–14463)

      Laure Théveau, Dr. Cécile Verrier, Pierrik Lassalas, Dr. Thibaut Martin, Prof. Dr. Georges Dupas, Dr. Olivier Querolle, Dr. Luc Van Hijfte, Prof. Dr. Francis Marsais and Dr. Christophe Hoarau

      Article first published online: 16 NOV 2011 | DOI: 10.1002/chem.201101615

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      Find the balance: Base-assisted non-concerted metallation–deprotonation (nCMD) and concerted metallation–deprotonation (CMD) were identified as significant operating mechanisms in palladium-catalysed direct C[BOND]H coupling with halides (see scheme). C2- and C5-selective CMD direct arylation procedures in a series of oxazole- and thiazole-4-carboxylates were designed by controlling the balance between electronic and steric factors.

    7. Glycolipids

      Chemical Synthesis of Helicobacter pylori Lipopolysaccharide Partial Structures and their Selective Proinflammatory Responses (pages 14464–14474)

      Dr. Atsushi Shimoyama, Akinori Saeki, Dr. Natsuko Tanimura, Prof. Hiroko Tsutsui, Prof. Kensuke Miyake, Prof. Yasuo Suda, Prof. Yukari Fujimoto and Prof. Koichi Fukase

      Article first published online: 16 NOV 2011 | DOI: 10.1002/chem.201003581

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      Inflammatory materials: Lipopolysaccharide (LPS) partial structures of Helicobacter pylori, including triacylated lipid A and Kdo-lipid A compounds, with or without the ethanolamine group at the 1-phosphate, were synthesized (see scheme). Stereoselective α-glycosylation of Kdo n-phenyltrifluoroacetimidate was achieved by microfluidic methods. Cytokine induction assays suggested a link between H. pylori LPS and chronic inflammation and atherosclerosis.

    8. Peroxidative Activity

      Characterization of G-Quadruplex/Hemin Peroxidase: Substrate Specificity and Inactivation Kinetics (pages 14475–14484)

      Xiaojuan Yang, Canliang Fang, Hongcheng Mei, Tianjun Chang, Dr. Zehui Cao and Prof. Dr. Dihua Shangguan

      Article first published online: 22 NOV 2011 | DOI: 10.1002/chem.201101941

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      Catalysis and inactivation: The binding of G-quadruplex (G4) and hemin greatly enhances the peroxidative activity of hemin. H2O2 withdraws two electrons from hemin to form a compound-I-like intermediate and/or other intermediates (see scheme). Eventually, the intermediates obtain electrons from the substrate or another H2O2 molecule to generate the original G4/hemin complex and oxidized products. Besides regenerating the original G4/hemin, the reaction of the active intermediates with H2O2 also causes degradation of a large number of intermediates.

    9. Energetic Materials

      3-Azido-N-nitro-1H-1,2,4-triazol-5-amine-Based Energetic Salts (pages 14485–14492)

      Kai Wang, Dr. Damon A. Parrish and Prof. Dr. Jean'ne M. Shreeve

      Article first published online: 23 NOV 2011 | DOI: 10.1002/chem.201102901

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      Nitrogen-rich energetic salts based on 3-azido-5-nitroamino-1,2,4-triazole exhibit promising detonation properties. Among these salts, hydroxylammonium 3-azido-5-nitroamino-1,2,4-triazolate is comparable to HMX in terms of detonation velocity and pressure, while hydrazinium 3-azido-5-nitroamino-1,2,4-triazolate has the most promise as a potentially applicable energetic material (see figure).

    10. Intramolecular Cycloaddition

      Intramolecular [2+2+2] Cycloaddition Reactions of Yne-ene-yne and Yne-yne-ene Enediynes Catalysed by RhI: Experimental and Theoretical Mechanistic Studies (pages 14493–14507)

      Dr. Anna Dachs, Dr. Anna Pla-Quintana, Dr. Teodor Parella, Prof. Miquel Solà and Prof. Anna Roglans

      Article first published online: 23 NOV 2011 | DOI: 10.1002/chem.201102210

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      [2+2+2] Cycloaddition reactions of two types of enediyne differing in the position of the double bond have been studied experimentally and theoretically. Enediynes of the type yne-ene-yne give standard [2+2+2] cyclohexadiene cycloadducts, whereas those of the type yne-yne-ene give isomers that differ from those that would be obtained by a standard [2+2+2] cycloaddition reaction (see figure).

    11. Molecular Recognition

      Conformer-Independent Ureidoimidazole Motifs—Tools to Probe Conformational and Tautomeric Effects on the Molecular Recognition of Triply Hydrogen-Bonded Heterodimers (pages 14508–14517)

      Maria L. Pellizzaro, Dr. Andrea M. McGhee, Lisa C. Renton, Dr. Michael G. Nix, Dr. Julie Fisher, Dr. W. Bruce Turnbull and Dr. Andrew J. Wilson

      Article first published online: 23 NOV 2011 | DOI: 10.1002/chem.201102128

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      Conformer independent arrays: This paper details the study of the conformer-independent ureidoimidazole donor–donor–acceptor (DDA) array and complementary amidoisocytosine (see figure), hexylamidocytosine and amidonaphthalene donor–acceptor–acceptor (DAA) arrays. It provides insight on the role of intramolecular hydrogen-bonding in mediating conformation, tautomeric configuration and dimerisation affinity within triply hydrogen-bonded heterodimers.

    12. Oligosaccharides

      A Highly α-Stereoselective Synthesis of Oligosaccharide Fragments of the Vi Antigen from Salmonella typhi and Their Antigenic Activities (pages 14518–14526)

      Lin Yang, Jingjing Zhu , Dr. Xiu-Jing Zheng, Prof. Guihua Tai and Prof. Xin-Shan Ye

      Article first published online: 17 NOV 2011 | DOI: 10.1002/chem.201102615

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      Synthetic carbohydrate vaccine: Di-, tri-, and tetrasaccharide fragments of the Vi antigen from Salmonella typhi were efficiently synthesized by exclusively α-stereoselective glycosylation reactions. The enzyme-linked immunosorbent assays (see figure; Vi-PS=Vi polysaccharide) showed that the tri and tetrasaccharides had much higher antigenic activities than those previously reported, demonstrating that the antigenic activities could be strengthened greatly by increasing the number of acetyl groups present.

    13. Cyclization Reactions

      Formal Homo-Nazarov and Other Cyclization Reactions of Activated Cyclopropanes (pages 14527–14538)

      Filippo De Simone, Tanguy Saget, Dr. Fides Benfatti, Sofia Almeida and Prof. Dr. Jérôme Waser

      Article first published online: 23 NOV 2011 | DOI: 10.1002/chem.201102583

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      Push and pull: The extension of the scope of cyclization reactions of donor–acceptor cyclopropanes with particular focus on the catalytic formal homo-Nazarov process is reported (see scheme). An ester group or a heteroatom was introduced on the cyclopropane to enhance its acceptor- or donor-mediated polarization. Control over regio- and diastereoselectivity was achieved, and a first proof of principle for asymmetric induction is described.

    14. Cyclization

      Conformational and Electronic Consequences in Crafting Extended, π-Conjugated, Light-Harvesting Macrocycles (pages 14539–14551)

      Dr. Leigh J. K. Boerner, Shivnath Mazumder, Dr. Maren Pink, Prof. Mu-Hyun Baik and Prof. Jeffrey M. Zaleski

      Article first published online: 14 NOV 2011 | DOI: 10.1002/chem.201102488

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      Plane, but not simple: Thermal Bergman cyclization of tetraalkynylporphyrins affords the dialkynylpicenoporphyrins in trace to 30 % yields, but no fully cyclized bispicenoporphyrin. DFT analysis shows that the barrier to the second cyclization is 5.5 kcal mol−1 higher than the first, increasing the likelihood that intermediates will follow alternate pathways (see figure). Thus, maintaining planarity is paramount for effective cyclization reactions in the pursuit of extended porphyrins.

    15. Nanofiber Arrays

      Controllable Growth of Conical and Cylindrical TiO2–Carbon Core–Shell Nanofiber Arrays and Morphologically Dependent Electrochemical Properties (pages 14552–14558)

      Dr. Rongsheng Chen , Liangsheng Hu , Prof. Kaifu Huo, Prof. Jijiang Fu, Prof. Hongwei Ni, Prof. Yan Tang and Prof. Paul K. Chu

      Article first published online: 22 NOV 2011 | DOI: 10.1002/chem.201102219

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      Quasi-aligned arrays of conical and cylindrical carbon-coated TiO2 nanofibers (NF) were controllably fabricated on Ti foils without any foreign metal catalyst or template. Their morphology-dependent electrochemical activities were evaluated, and the conical NFs, with their higher density of exposed edge planes or free graphene-sheet ends, exhibit better electrochemical performance, which allows sensitive analysis of uric acid (UA) in the presence of ascorbic acid (AA; see figure).

    16. Hydroaminomethylation

      Highly Regioselective Hydroaminomethylation of Terminal Olefins to Linear Amines Using Rh Complexes with a Tetrabi Phosphorus Ligand (pages 14559–14563)

      Guodu Liu, Kexuan Huang, Chaoxian Cai, Bonan Cao, Mingxin Chang, Prof. Wenjun Wu and Prof. Xumu Zhang

      Article first published online: 21 NOV 2011 | DOI: 10.1002/chem.201103073

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      On the right lines: A highly regioselective hydroaminomethylation of terminal olefins catalyzed by Rh complexes with a Tetrabi phosphorus ligand has been developed. By using this methodology, a variety of terminal olefins and secondary amines are compatible in the reaction; in general, aliphatic olefins and secondary amines give the corresponding linear amines with a high degree of chemoselectivity, regioselectivity, and amine yield (see scheme).

    17. Supramolecular Chemistry

      Supramolecular Inclusion Complexes of Two Cyclic Zinc Bisporphyrins with C60 and C70: Structural, Thermodynamic, and Photophysical Characterization (pages 14564–14577)

      Dr. Laura P. Hernández-Eguía, Eduardo C. Escudero-Adán, Dr. Inmaculada C. Pintre, Dr. Barbara Ventura, Dr. Lucia Flamigni and Prof. Dr. Pablo Ballester

      Article first published online: 17 NOV 2011 | DOI: 10.1002/chem.201101511

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      Fullerene sandwiched: The formation in solution of inclusion complexes between macrocyclic zinc bisporphyrins and fullerenes C60 and C70 is described and their solid-state structures are reported (see figure). The complexes are highly thermodynamically stable, and energy-transfer and electron-transfer processes occur between their components. Charge-separated states characterized by a reduced fullerene and an oxidized porphyrin radical are detected.

    18. C[BOND]H activation

      An Unusual Organoyttrium Alkyl Complex Containing a [C5HMe33-CH2)-C5H4N-κ] Ligand and an Elusive Cyclopentadienide-Based Scandium Tuck-Over Zwitterion Obtained by C[BOND]H Bond Activation (pages 14578–14585)

      Zhongbao Jian and Prof. Dr. Dongmei Cui

      Article first published online: 14 NOV 2011 | DOI: 10.1002/chem.201102378

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      Ligand facelift: The first yttrium mono(alkyl) complex containing an unusual [C5HMe33-CH2)-C5H4N-κ] ligand was synthesized by methyl C[BOND]H bond activation (see scheme). More remarkably, the first cyclopentadienide-based scandium zwitterionic “tuck-over” complex incorporating an unprecedented [η5:κ-C5Me31-CH2)-C5H4N]2− dianionic ligand was successfully obtained.

    19. Hydrogen Storage

      Do Rhodium Bis(σ-amine-borane) Complexes Play a Role as Intermediates in Dehydrocoupling Reactions of Amine-boranes? (pages 14586–14592)

      Valeria Butera, Prof. Nino Russo and Prof. Dr. Emilia Sicilia

      Article first published online: 22 NOV 2011 | DOI: 10.1002/chem.201102365

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      Dehydrocoupling at a Rh center: DFT was used to investigate the mechanism of dehydrogenation and coupling of dimethylamine-borane (Me2HNBH3) for a Rh complex with an unusual bis(σ-amine-borane) binding mode (see figure). Calculations were carried out to probe whether such binding motifs play a role in determining the general course of amine-borane dehydrocoupling reactions.

    20. Homogeneous Catalysis

      Iron-Mediated and -Catalyzed Metalative Cyclization of Electron-Withdrawing-Group-Substituted Alkynes and Alkenes with Grignard Reagents (pages 14593–14602)

      Dr. Takeshi Hata, Shiro Sujaku, Naoki Hirone, Kirihiro Nakano, Junsuke Imoto, Haduki Imade and Prof. Dr. Hirokazu Urabe

      Article first published online: 23 NOV 2011 | DOI: 10.1002/chem.201101273

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      Convenient iron: Iron reagents generated from FeCl2 and RMgX (4 equiv) are utilized for the metalation of functionalized alkynes and alkenes, which subsequently enable the preparation of various kinds of cyclic products (see scheme). In enyne cyclizations the quantity of the iron salt can be reduced to catalytic levels.

    21. Crystal Growth

      Microwave-Induced Formation of Platinum Nanostructured Networks with Superior Electrochemical Activity and Stability (pages 14603–14610)

      Prof. Dr. Falong Jia, Fangfang Wang, Yun Lin and Prof. Dr. Lizhi Zhang

      Article first published online: 10 NOV 2011 | DOI: 10.1002/chem.201101179

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      Growing together is powerful! Special Pt nanostructured networks, formed by the assembly of Pt nanocrystals, were synthesized by a surfactant-free microwave-induced approach, and were found to exhibit superior catalytic activity and stability arising from the special network structure and abundant defects formed during the microwave-induced aggregation process (see picture). Benzyl alcohol and microwave irradiation were demonstrated to be crucial for the assembly of Pt nanocrystals in a short time.

    22. Luminescence

      Quenching of the Luminescence of Upconverting Luminescent Nanoparticles by Heavy Metal Ions (pages 14611–14617)

      Sayed M. Saleh, Reham Ali and Prof. Dr. Otto S. Wolfbeis

      Article first published online: 21 NOV 2011 | DOI: 10.1002/chem.201101860

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      The red and green luminescence of upconverting luminescent nanoparticles (photoexcited with a 980 nm diode laser) is dynamically and statically quenched by heavy metal ions, in particular by HgII ions (see figure).

    23. Zeolites

      Hierarchical Mesoporous Zeolites: Direct Self-Assembly Synthesis in a Conventional Surfactant Solution by Kinetic Control over the Zeolite Seed Formation (pages 14618–14627)

      Dr. Yan Zhu, Dr. Zile Hua, Dr. Jian Zhou, Dr. Lijun Wang, Dr. Jinjin Zhao, Dr. Yun Gong, Wei Wu, Meiling Ruan and Prof. Jianlin Shi

      Article first published online: 14 NOV 2011 | DOI: 10.1002/chem.201101401

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      Subnanocrystals were used as zeolite seeds for the synthesis of hierarchical mesoporous zeolites under the direction of hexadecyl trimethyl ammonium bromide (CTAB; see scheme). Different interaction models between mesoporogen and zeolite precursor were subject to kinetics.

    24. Mechanisms of Oligomerization

      Neutral Nickel Oligo- and Polymerization Catalysts: The Importance of Alkyl Phosphine Intermediates in Chain Termination (pages 14628–14642)

      Wouter Heyndrickx, Dr. Giovanni Occhipinti, Yury Minenkov and Prof. Dr. Vidar R. Jensen

      Article first published online: 16 NOV 2011 | DOI: 10.1002/chem.201101152

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      Nickel-catalyzed polymerization: DFT calculations for nickel-catalyzed oligo- and polymerizations have demonstrated that an unconventional chain-termination reaction (see scheme) is responsible for a range of experimental observations, such as the decrease in polymer molecular weight with increasing phosphine concentration/basicity and the SHOP (Shell higher olefin process)-type catalyst's ability to produce linear α-olefins from ethylene.

    25. Energy Transfer

      Design and Photophysical Properties of Zinc(II) Porphyrin-Containing Dendrons Linked to a Central Artificial Special Pair (pages 14643–14662)

      Dr. Frédérique Brégier, Shawkat M. Aly, Prof. Claude P. Gros, Dr. Jean-Michel Barbe, Dr. Yoann Rousselin and Prof. Pierre D. Harvey

      Article first published online: 14 NOV 2011 | DOI: 10.1002/chem.201101832

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      Transfer protocol: Dendrimers composed of a cofacial bis[copper(II) porphyrin] and zinc(II) porphyrin dendrons (Gx; x=1–3) were prepared by using click chemistry and their photophysical properties were studied. S1–T1 and T1–T1 energy transfers (ETs; see scheme) explain the decrease in emission lifetimes of the respective donors. The amplitude of the transfer rate constants indicates that chain folding brings the antennas closer to the core.

    26. Nanotechnology

      Selective Adsorption of Proteins on Single-Wall Carbon Nanotubes by Using a Protective Surfactant (pages 14663–14671)

      Dr. Anton Knyazev, Loïc Louise, Dr. Michèle Veber, Dr. Dominique Langevin, Dr. Arianna Filoramo, Dr. Adriele Prina-Mello and Dr. Stéphane Campidelli

      Article first published online: 17 NOV 2011 | DOI: 10.1002/chem.201101182

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      Simple, yet selective control: The control of the adsorption of proteins on the sidewalls of carbon nanotubes by using proper functionalization (either covalent or noncovalent) is demonstrated. Our approach is simple, straightforward, and suitable for the selective coupling of other biomolecules that contain thio or amino groups onto nanotubes (see scheme; BSA=borine serum albumin, SWNT=single-wall carbon nanotubes).

    27. Polycycles

      Lateral Extension of π Conjugation along the Bay Regions of Bisanthene through a Diels–Alder Cycloaddition Reaction (pages 14672–14680)

      Jinling Li, Chongjun Jiao, Prof. Kuo-Wei Huang and Prof. Jishan Wu

      Article first published online: 14 NOV 2011 | DOI: 10.1002/chem.201102120

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      Expanded and twisted! Diels–Alder (D–A) cycloaddition at the bay regions of bisanthene gave a series of expanded quinones (see scheme). Subsequent nucleophilic addition and reductive aromatization led to new, laterally expanded and twisted, polycyclic aromatic hydrocarbons with near-infrared absorption and emission.

    28. Solar Cells

      Copolymers Comprising 2,7-Carbazole and Bis-benzothiadiazole Units for Bulk-Heterojunction Solar Cells (pages 14681–14688)

      Jonggi Kim, Myoung Hee Yun, Piyush Anant, Prof. Shinuk Cho, Dr. Josemon Jacob, Prof. Jin Young Kim and Prof. Changduk Yang

      Article first published online: 14 NOV 2011 | DOI: 10.1002/chem.201101258

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      Influence on photovoltaic characteristics: A family of donor (D)–acceptor (A) conjugated polymers based on bis-benzothiadiazole (BBT), namely PCZ-BBT, PCZV-BBTV, and PDTCZ-BBT, are presented for use in bulk-heterojunction solar cells. Both the HOMO and LUMO of the resulting polymers are found to be deeper lying than those of benzothiadiazole-based polymers.

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      Preview: Chem. Eur. J. 52/2011 (page 14691)

      Article first published online: 14 DEC 2011 | DOI: 10.1002/chem.201190264

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