Chemistry - A European Journal

Cover image for Vol. 18 Issue 21

May 21, 2012

Volume 18, Issue 21

Pages 6401–6691

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Concept
    8. Communications
    9. Full Papers
    10. Preview
    1. You have free access to this content
      Cover Picture: Saccharide-Modified Nanodiamond Conjugates for the Efficient Detection and Removal of Pathogenic Bacteria (Chem. Eur. J. 21/2012) (page 6401)

      Dr. Mirja Hartmann, Patrick Betz, Yuchen Sun, Prof. Dr. Stanislav N. Gorb, Prof. Dr. Thisbe K. Lindhorst and Prof. Dr. Anke Krueger

      Article first published online: 15 MAY 2012 | DOI: 10.1002/chem.201290083

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      A carbohydrate-modifiednanodiamond is a valuable new material for the straightforward detection and efficient removal of pathogenic bacteria from polluted water sources. It is nontoxic and can readily be used in difficult environments. Furthermore, sugar specificity of bacterial surface proteins allows for identification and targeted sectioning of particular virulent strains through tailored glycosylation of the nanodiamond surface. For more details see the Full Paper by A. Krueger, T. K. Lindhorst et al. on page 6485 ff.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Concept
    8. Communications
    9. Full Papers
    10. Preview
    1. Inside Cover: The Role of Pendant Amines in the Breaking and Forming of Molecular Hydrogen Catalyzed by Nickel Complexes (Chem. Eur. J. 21/2012) (page 6402)

      Dr. Simone Raugei, Dr. Shentan Chen, Dr. Ming-Hsun Ho, Dr. Bojana Ginovska-Pangovska, Dr. Roger J. Rousseau, Dr. Michel Dupuis, Dr. Daniel L. DuBois and Dr. R. Morris Bullock

      Article first published online: 15 MAY 2012 | DOI: 10.1002/chem.201290084

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      Pendant amines incorporated in the second coordination sphere of nickel bis(diphosphine) catalysts for H2 oxidation and H2 production play a crucial role in the breaking and forming of the H[BOND]H bond of molecular hydrogen. An accurate and comprehensive theoretical study is reported in the Full Paper by S. Raugei et al. on page 6493 ff., which allows for a deeper atomistic understanding, that will guide the design of more efficient electrocatalysts for the intercorversion between electrical energy and fuels.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Concept
    8. Communications
    9. Full Papers
    10. Preview
    1. Graphical Abstract: Chem. Eur. J. 21/2012 (pages 6405–6414)

      Article first published online: 15 MAY 2012 | DOI: 10.1002/chem.201290085

  4. Corrigendum

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Concept
    8. Communications
    9. Full Papers
    10. Preview
    1. You have free access to this content
  5. News

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

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

      Rapid Perturbation of Free-Energy Landscapes: From In Vitro to In Vivo (pages 6420–6427)

      Hannah Gelman, Dr. Max Platkov and Prof. Martin Gruebele

      Article first published online: 19 APR 2012 | DOI: 10.1002/chem.201104047

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      New frontiers: Molecular biophysics has been used to investigate the dynamics of biomolecular reactions by rapid perturbation in vitro for more than a half century. Modern-day imaging and labeling techniques allow for the application of these methods in vivo. This new frontier will provide insight into the active and passive methods used by the cell to regulate protein function, protein–RNA binding and many other biomolecular interactions, connecting the molecular level to the systems biology of the cell.

  7. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Concept
    8. Communications
    9. Full Papers
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    1. Intramolecular Cycloaddition

      Convenient Syntheses and Photophysical Properties of 1-Thio- and 1-Seleno-1,3-Butadiene Fluorophores in Rigid Dibenzobarrelene and Benzobarrelene Skeletons (pages 6428–6432)

      Prof. Dr. Akihiko Ishii, Tatsuro Annaka and Dr. Norio Nakata

      Article first published online: 19 APR 2012 | DOI: 10.1002/chem.201200761

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      No heavy-atom effect: Highly fluorescent, sulfur- or selenium-containing compounds were synthesized by intramolecular [4+2]-cycloadditions between 9-anthryl or 1-naphthyl and alkynyl moieties (see scheme). Their fluorescence is based on a 1-chalcogeno-1,3-butadiene-conjugated system in a rigid skeleton. Some of them are also highly fluorescent in the solid state. The monoxide of Mbb-S is more fluorescent in the solid state (ΦF=0.6) than in solution (ΦF<0.02).

    2. Cage Compounds

      Tuning the Electronic and Spin Complexity in Organic–Inorganic Molecular Hybrid Compounds (pages 6433–6436)

      Dr. Jabor Rabeah, Prof. Dr. Reinhard Stößer, Dr. Haijun Jiao, Prof. Dr. Sergey I. Troyanov, Dr. Jörg Radnik, Dr. Helmut Dwelk, Prof. Dr. Manfred Meisel and Prof. Dr. Angelika Brückner

      Article first published online: 19 APR 2012 | DOI: 10.1002/chem.201200931

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      Caught by the cage: New vanadium phosphonate cages with a fluoride template inside and charge-compensating transition-metal cations outside were prepared in a simple way. The charge and ligand sphere of the cation govern its interaction with the cage and can be used to modify the magnetic and redox properties of the cage, which also depend on the anionic template (see figure).

    3. Fluorescence

      Isoindole-BODIPY Dyes as Red to Near-Infrared Fluorophores (pages 6437–6442)

      Changjiang Yu, Yajun Xu, Prof. Dr. Lijuan Jiao, Jinyuan Zhou, Zhaoyun Wang and Prof. Dr. Erhong Hao

      Article first published online: 19 APR 2012 | DOI: 10.1002/chem.201200398

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      Three-in-one go: One-pot synthesis of isoindole-BODIPY dyes was developed based on nucleophilic substitution (SNAr) reactions of in situ formed chlorinated dipyrromethene by pyrrole. These dyes have long wavelengths, sharp absorption and fluorescence, high fluorescence quantum yields, and high photostability. The wavelength is finely tunable over a wide range (590–714 nm) by variation of substituent groups and functionalization (see scheme).

    4. Electron Transfer

      Large Increase of the Lifetime of a Charge-Separated State in a Molecular Triad Induced by Hydrogen-Bonding Solvent (pages 6443–6447)

      Jihane Hankache and Prof. Dr. Oliver S. Wenger

      Article first published online: 25 APR 2012 | DOI: 10.1002/chem.201200199

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      Life of triad: The lifetime of a charge-separated state (see figure) increases from about 50 to 2000 ns when the solvent is changed from aprotic CH2Cl2 to the strong hydrogen-bond donor hexafluoroisopropanol.

    5. Insertion Reactions

      Reversible 1,4-Insertion of Pyridine Into a Highly Polar Metal–Carbon Bond: Effect of the Second Metal (pages 6448–6452)

      Dipl.-Chem. Crispin Lichtenberg, Dr. Thomas P. Spaniol, Dr. Lionel Perrin, Prof. Dr. Laurent Maron and Prof. Dr. Jun Okuda

      Article first published online: 19 APR 2012 | DOI: 10.1002/chem.201200808

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      Highly polar allylpotassium reacts with pyridine in a reversible 1,4-insertion to give an unstable N-metalated dihydropyridine (DHP). The N-metalated DHP can be stabilized by conversion into the corresponding potassium zincate or magnesate maintaining the reversible character of the insertion reaction (see scheme).

    6. Cyanation

      Synthesis of Acrylonitriles through an FeCl3-Catalyzed Domino Propargylic Substitution/Aza-Meyer–Schuster Rearrangement Sequence (pages 6453–6456)

      Lu Hao, Feng Wu, Zong-Cang Ding, Su-Xia Xu, Yan-Li Ma, Prof. Dr. Li Chen and Prof. Dr. Zhuang-Ping Zhan

      Article first published online: 24 APR 2012 | DOI: 10.1002/chem.201200763

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      Nontoxic cyanide source: An unprecedented route to acrylonitriles by employing propargylic alcohols and para-tolylsulfonohydrazide as a combined cyano source has been developed (see scheme). This efficient and practical cyanation reaction proceeds through an FeCl3-catalyzed domino propargylic substitution/aza-Meyer–Schuster rearrangement sequence, the rearrangement process of which is reported for the first time.

    7. Phosphorescence

      Comparison of Tetraphenylmethane and Tetraphenylsilane as Core Structures of High-Triplet-Energy Hole- and Electron-Transport Materials (pages 6457–6461)

      Prof. Chil Won Lee and Prof. Jun Yeob Lee

      Article first published online: 18 APR 2012 | DOI: 10.1002/chem.201103640

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      Tetraphenylmethane and tetraphenylsilane were compared as building units for high-triplet-energy, charge-transport materials. Tetraphenylsilane is effective as the building unit in electron-transport materials, whereas tetraphenylmethane is suitable in hole-transport materials (see figure; TSPO1=diphenylphosphine oxide-4-(triphenylsilyl), TSPA=phenyl-N,N-diphenyl-4-(triphenylsilyl)aniline, and TCPA=N,N-diphenyl-4-tritylaniline).

    8. Crystal Engineering

      Confused HCl: Hydrogen Chloride or Hydrochloric Acid? (pages 6462–6464)

      Dr. Sathyanarayana Reddy Perumalla and Dr. Changquan Calvin Sun

      Article first published online: 16 APR 2012 | DOI: 10.1002/chem.201103669

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      Hydrogen chloride can exist in various forms. Indiscriminative uses of the abbreviation “HCl” for its different forms has led to considerable confusion in the literature. The discovery of hidden solid forms of widely studied molecules by using different forms of hydrogen chloride highlights the need of clarifying the terminology surrounding hydrogen chloride in chemical research (see figure).

    9. Olefin Metathesis

      Ruthenium–Amido Complexes: Synthesis, Structure, and Catalytic Activity in Olefin Metathesis (pages 6465–6469)

      Dr. Cezary Pietraszuk, Dr. Szymon Rogalski, Beata Powała, Miłosz Miętkiewski, Dr. Maciej Kubicki, Grzegorz Spólnik, Prof. Dr. Witold Danikiewicz, Krzysztof Woźniak, Aleksandra Pazio, Dr. Anna Szadkowska, Anna Kozłowska and Prof. Dr. Karol Grela

      Article first published online: 18 APR 2012 | DOI: 10.1002/chem.201103973

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      Unprecedented amido derivatives of the first-, second-, and third-generation Grubbs ruthenium catalysts were prepared, characterized, and tested in ring-closing metathesis (RCM) of model dienes. In the ruthenium–amide (formally: 2-ruthenaindole) form, these complexes exhibit nearly no activity in RCM. However, a dramatic increase of activity was observed upon in situ activation with an ethereal solution of HCl (see figure).

    10. Isomerization

      Brønsted Acid Catalyzed Cycloisomerizations of 5,2-Enyne-1-ones: Highly Regioselective Synthesis of 2,3-Dihydro-4H-pyran-4-ones (pages 6470–6474)

      Dr. Fang Yang, Ke-Gong Ji, Shu-Chun Zhao, Shaukat Ali, Yu-Ying Ye, Xue-Yuan Liu and Prof. Dr. Yong-Min Liang

      Article first published online: 18 APR 2012 | DOI: 10.1002/chem.201103771

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      Dual-action catalyst: A Brønsted acid catalyzed regioselective cycloisomerization was found to be highly effective for the preparation of structurally diverse 2,3-dihydro-4H-pyran-4-ones in a 6-exo-trig manner from the corresponding 5,2-enyne-1-ones. In this reaction, the Brønsted acid acts as a dual catalyst activating both the carbonyl and alkene moieties in a cascade manner (see scheme).

  8. Full Papers

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

      How Charging Corannulene with One and Two Electrons Affects Its Geometry and Aggregation with Sodium and Potassium Cations (pages 6476–6484)

      Dr. Alexander V. Zabula, Sarah N. Spisak, Dr. Alexander S. Filatov, Dr. Vladimir M. Grigoryants and Prof. Dr. Marina A. Petrukhina

      Article first published online: 26 APR 2012 | DOI: 10.1002/chem.201200416

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      Adding metals to a bowl: Mono- and dianions of corannulene have been isolated in the form of their salts with sodium and potassium ions in the presence of [18]crown-6 ether. Single-crystal X-ray diffraction studies reveal the geometrical perturbations of the corannulene core upon stepwise electron acquisition and various metal-ion binding modes. UV/Vis, ESR, and NMR spectroscopy investigations demonstrate different environments of the bowl-shaped anions in solution (see figure).

    2. Carbohydrates

      Saccharide-Modified Nanodiamond Conjugates for the Efficient Detection and Removal of Pathogenic Bacteria (pages 6485–6492)

      Dr. Mirja Hartmann, Patrick Betz, Yuchen Sun, Prof. Dr. Stanislav N. Gorb, Prof. Dr. Thisbe K. Lindhorst and Prof. Dr. Anke Krueger

      Article first published online: 23 APR 2012 | DOI: 10.1002/chem.201104069

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      Sweet diamond: Novel nanodiamond–saccharide conjugates have been synthesized and applied for the detection and removal of pathogenic bacteria. A new sandwich assay enables this detection by specific and nonspecific interactions by using agglutinating nanoparticles. The specific flocculation of nanodiamond–mannose conjugates with bacteria was used for the efficient and repeated removal of these germs from water samples (see scheme).

    3. Reaction Mechanisms

      The Role of Pendant Amines in the Breaking and Forming of Molecular Hydrogen Catalyzed by Nickel Complexes (pages 6493–6506)

      Dr. Simone Raugei, Dr. Shentan Chen, Dr. Ming-Hsun Ho, Dr. Bojana Ginovska-Pangovska, Dr. Roger J. Rousseau, Dr. Michel Dupuis, Dr. Daniel L. DuBois and Dr. R. Morris Bullock

      Article first published online: 25 APR 2012 | DOI: 10.1002/chem.201103346

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      Pendant amines! The presence of pendant amines in nickel diphosphine electrocatalysts greatly facilitates the heterolytic cleavage of H2 in catalysts for oxidation of H2, by effectively helping to shuttle protons, making H2 evolution a very facile process. By using ab initio molecular dynamics simulations, an extensive analysis of the structural and electronic features governing the catalytic efficiency of this class of catalysts has been carried out.

    4. Asymmetric Hydrogenation

      Chiral Hetero- and Carbocyclic Compounds from the Asymmetric Hydrogenation of Cyclic Alkenes (pages 6507–6513)

      J. Johan Verendel, Jia-Qi Li, Xu Quan, Byron Peters, Taigang Zhou, Dr. Odd R. Gautun, Prof. Thavendran Govender and Prof. Pher G. Andersson

      Article first published online: 24 APR 2012 | DOI: 10.1002/chem.201104073

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      Several types of chiral hetero- and carbocyclic compounds have been synthesized by asymmetric hydrogenation of cyclic alkenes by using N,P-ligated iridium catalysts (see scheme). Six-membered cyclic alkenes were reduced in good to excellent selectivity, whereas the reduction of five-membered cyclic alkenes was generally less selective. The major enantiomer formed could be predicted from a selectivity model and isomeric alkenes gave complementary enantioselectivity.

    5. Electrodes

      Electrochemistry of Nanocrystalline 3C Silicon Carbide Films (pages 6514–6519)

      Dr. Nianjun Yang, Dr. Hao Zhuang, René Hoffmann, Dr. Waldemar Smirnov, Jakob Hees, Prof. Xin Jiang and Dr. Christoph E. Nebel

      Article first published online: 13 APR 2012 | DOI: 10.1002/chem.201103765

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      Film studies: The electrochemical properties of nanocrystalline 3C silicon carbide films have been investigated in detail for the first time. The results confirm that the film is a promising electrode material (see figure).

    6. Protein–Protein Interactions

      An Optimised Small-Molecule Stabiliser of the 14-3-3–PMA2 Protein–Protein Interaction (pages 6520–6527)

      Dr. Anja Richter, Dr. Rolf Rose, Dr. Christian Hedberg, Prof. Dr. Herbert Waldmann and Dr. Christian Ottmann

      Article first published online: 29 MAR 2012 | DOI: 10.1002/chem.201103761

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      Glued together: An initial screening hit that stabilises a 14-3-3 protein–protein interaction has been optimised by means of chemical synthesis. The resulting compound is three-times more active than the initial hit and displays selectivity for the interaction of 14-3-3 proteins with the plant proton pump PMA2 (see figure).

    7. Drug Discovery

      Design, Synthesis and Biological Evaluation of Potent Azadipeptide Nitrile Inhibitors and Activity-Based Probes as Promising Anti-Trypanosoma brucei Agents (pages 6528–6541)

      Peng-Yu Yang, Min Wang, Dr. Lin Li, Hao Wu, Dr. Cynthia Y. He and Prof. Dr. Shao Q. Yao

      Article first published online: 4 APR 2012 | DOI: 10.1002/chem.201103322

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      Killer instinct: We report the design, synthesis, and evaluation of a series of azanitriles as highly potent inhibitors against recombinant cruzain and rhodesain and the growth of T. brucei parasites (see figure). Selected hit compounds were then converted into activity-based probes and used for parasite-based proteome profiling to further elucidate potential cellular targets. Bioimaging experiments with these probes were carried out to study cellular uptake and subcellular distribution of the compounds in T. brucei.

    8. Dendrimers

      Formation of Columnar Liquid Crystals on the Basis of Unconventional Triazine-Based Dendrimers by the C3-Symmetric Approach (pages 6542–6547)

      Prof. Dr. Long-Li Lai, Shun-Ju Hsu, Hui-Chu Hsu, Sheng-Wei Wang, Dr. Kung-Lung Cheng, Chun-Jung Chen, Tsai-Hui Wang and Prof. Dr. Hsiu-Fu Hsu

      Article first published online: 4 APR 2012 | DOI: 10.1002/chem.201103423

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      C2- and C3-symmetric dendrimers based on triazine were designed and prepared. The C3-symmetric compounds (see figure) displayed columnar liquid-crystalline phases, but C2-symmetric dendrimers did not behave analogously, and this difference is reasonably explained by molecular-mechanics calculations. This new strategy should be applicable to other types of dendrimers with rigid frameworks for preparing columnar liquid crystals.

    9. Carbohydrate Microarrays

      Preparation of Carbohydrate Arrays by Using Diels–Alder Reactions with Inverse Electron Demand (pages 6548–6554)

      Dr. Henning S. G. Beckmann, Dipl.-Chem. Andrea Niederwieser, Prof. Dr. Manfred Wiessler and Prof. Dr. Valentin Wittmann

      Article first published online: 18 APR 2012 | DOI: 10.1002/chem.201200382

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      Served on a plate: Chemoselective immobilization of synthetic dienophile–carbohydrate conjugates has been achieved on tetrazine-derivatized glass slides by employing Diels–Alder reactions with inverse electron demand. By using a bifunctional linker, unmodified reducing oligosaccharides can also be selectively tagged with a dienophile and subsequently immobilized (see figure).

    10. Oxygen Activation

      Electronic Structure Analysis of the Oxygen-Activation Mechanism by FeII- and α-Ketoglutarate (αKG)-Dependent Dioxygenases (pages 6555–6567)

      Dr. Shengfa Ye, Christoph Riplinger, Andreas Hansen, Prof. Dr. Carsten Krebs, Prof. Dr. J. Martin Bollinger Jr. and Prof. Dr. Frank Neese

      Article first published online: 18 APR 2012 | DOI: 10.1002/chem.201102829

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      Activation analysis: A detailed analysis of the electronic-structure changes that occur during oxygen activation by FeII- and α-ketoglutarate (αKG)-dependent dioxygenases has been performed (see figure). This allowed the rationalization of the distinct shapes of potential-energy surfaces with different spin multiplicities and gain insight into the biological function of cosubstrate αKG.

    11. Photochromism

      Gated Photochromism and Acidity Photomodulation of a Diacid Dithienylethene Dye (pages 6568–6575)

      Julie Massaad, Dr. Jean-Claude Micheau, Dr. Christophe Coudret, Dr. Rafael Sanchez, Prof. Gonzalo Guirado and Prof. Stéphanie Delbaere

      Article first published online: 11 APR 2012 | DOI: 10.1002/chem.201103896

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      Minisize, multipurpose: A pH-sensitive photochromic diarylethene was studied according to chemical-dynamic methodology. Quantitative data about its photochromic reactivity and acid–base properties were successfully extracted from its photocoloration and titration in acetonitrile. Although structurally extremely simple, the compound already shows a rich variety of behaviors (see scheme).

    12. Gold Catalysis

      Gold(I)-Catalyzed Rearrangement of 3-Silyloxy-1,5-enynes: An Efficient Synthesis of Benzo[b]thiophenes, Dibenzothiophenes, Dibenzofurans, and Indole Derivatives (pages 6576–6580)

      Prof. Dr. A. Stephen K. Hashmi, Weibo Yang and Dr. Frank Rominger

      Article first published online: 19 APR 2012 | DOI: 10.1002/chem.201200314

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      Golden rings: Benzanellated heterocycles are conveniently accessible by a gold(I)-catalyzed intramolecular cyclization. The tandem 5-endo-dig cyclization/2,3-shift places the heteroatom X in ortho position of the aryl group on the newly formed benzene ring (see scheme).

    13. Antitumor Agents

      Deciphering the Activation Sequence of Ferrociphenol Anticancer Drug Candidates (pages 6581–6587)

      Pierluca Messina, Prof. Eric Labbé, Dr. Olivier Buriez, Dr. Elizabeth A. Hillard, Dr. Anne Vessières, Didier Hamels, Dr. Siden Top, Prof. Gérard Jaouen, Dr. Yves Michel Frapart, Prof.Dr. Daniel Mansuy and Prof. Dr. Christian Amatore

      Article first published online: 11 APR 2012 | DOI: 10.1002/chem.201103378

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      Model behavior: The complete oxidation sequence of a model for ferrociphenols, a new class of anticancer drug candidates, is reported (see scheme). A combination of cyclic voltammetry, EPR spectroscopy, and 1H and 13C NMR spectroscopy was used to monitor and characterize the different species along the pathway.

    14. Organic Explosives

      En Route to Dinitroacetylene: Nitro(trimethylsilyl)acetylene and Nitroacetylene Harnessed by Dicobalt Hexacarbonyl (pages 6588–6603)

      Dr. G. Kenneth Windler, Dr. Mao-Xi Zhang, Robert Zitterbart, Dr. Philip F. Pagoria and Prof. K. Peter C. Vollhardt

      Article first published online: 24 APR 2012 | DOI: 10.1002/chem.201200473

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      Explosives on a leash: Highly sensitive nitroacetylene and nitro(trimethylsilyl)acetylene can be stabilized as their [Co2(CO)6] complexes, the structures of which are characterized crystallographically (see figure). This finding opens the door to applications of nitroalkynes in synthesis.

    15. Biocatalysis

      Continuous-Flow Reactor-Based Enzymatic Synthesis of Phosphorylated Compounds on a Large Scale (pages 6604–6609)

      Lara Babich, Aloysius F. Hartog, Dr. Michael A. van der Horst and Prof. Dr. Ron Wever

      Article first published online: 13 APR 2012 | DOI: 10.1002/chem.201200101

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      Phosphorylation made easy: Acid phosphatase was covalently immobilized on polymethacrylate beads with an epoxy linker (see scheme). The beads were used in a fed batch and in a small continuous-flow packed-bed reactor to prepare D-glucose-6-phosphate, N-acetyl-D-glucosamine-6-phosphate, allyl phosphate, dihydroxyacetone phosphate, glycerol-1-phosphate, and inosine-5′-monophosphate on a gram scale.

    16. Reaction Mechanisms

      Insight into the Reaction Mechanisms of (MeC5H4)3U with Isoelectronic Heteroallenes CS2, COS, PhN3, and PhNCO by DFT Studies: A Unique Pathway that Involves Bimetallic Complexes (pages 6610–6615)

      Ludovic Castro and Prof. Dr. Laurent Maron

      Article first published online: 18 APR 2012 | DOI: 10.1002/chem.201103754

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      U are always on my mind: The mechanisms for the reactions of four isoelectronic heteroallenes (see figure) with the trivalent uranium complex (MeC5H4)3U were determined by DFT methods. The unique reaction mechanism involved a uranium(IV) bimetallic complex with a bridged heteroallene intermediate.

    17. Mechanistic Origin of Antagonist Effects of Usual Anionic Bases (OH, CO32−) as Modulated by their Countercations (Na+, Cs+, K+) in Palladium-Catalyzed Suzuki–Miyaura Reactions (pages 6616–6625)

      Dr. Christian Amatore, Dr. Anny Jutand and Gaëtan Le Duc

      Article first published online: 18 APR 2012 | DOI: 10.1002/chem.201200516

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      Not that innocent: Unexpectedly, some countercations (Na+, Cs+, K+) of the anionic bases used in the Suzuki–Miyaura reactions decelerate the transmetalation reaction in comparison with inert countercations, such as nBu4N+, due to a competitive complexation of the reactive ArPd(OH)(PPh3)2 by M+ (see scheme).

    18. Medium-Ring Compounds

      Medium-Sized Rings versus Macrocycles through Rhodium-Catalyzed Ring-Expansion Reactions of Cyclic Acetals (pages 6626–6631)

      Dr. Rafael Ballesteros-Garrido, Dr. Diane Rix, Dr. Céline Besnard and Prof. Jérôme Lacour

      Article first published online: 11 APR 2012 | DOI: 10.1002/chem.201103870

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      Medium rings: α-Diazo β-ketoesters and diketones react with cyclic acetals under RhII catalysis to yield unprecedented polyoxygenated 8- and 9-membered rings in one pot (see scheme). The reactions occur under mild conditions with yields up to 90 %. The medium-sized ring formation and perfect regioselectivity are direct consequences of Baldwin's rules.

    19. Copolymers

      Highly Hydrophilic Copolymers of N,N-Dimethylacrylamide, Acrylamido-2-methylpropanesulfonic acid, and Ethylenedimethacrylate: Nanoscale Morphology in the Swollen State and Use as Exotemplates for Synthesis of Nanostructured Ferric Oxide (pages 6632–6643)

      Dr. Paolo Centomo, Karel Jeřábek, Davide Canova, Dr. Alfonso Zoleo, Prof. Anna Lisa Maniero, Dr. Alessandro Sassi, Dr. Patrizia Canton, Prof. Benedetto Corain and Prof. Marco Zecca

      Article first published online: 29 MAR 2012 | DOI: 10.1002/chem.201102359

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      Swellable cross-linked copolymers of N,N-dimethylacrylamide, acrylamido-2-methylpropanesulfonic acid, and ethylenedimethacrylate (see schematic chemical structure) were prepared. The highly expanded polymer framework in the water-swollen state was used as a template for growth of nanostructured hematite. SEM-EDX measurements revealed that the sulfur of the functional monomer and the iron of the nanoparticles are both homogeneously distributed within the resin particles (see picture).

    20. Jahn–Teller distortion

      Halogenated Benzene Cation Radicals (pages 6644–6654)

      Matthias J. Molski, Doreen Mollenhauer, Sebastian Gohr, Prof. Dr. Beate Paulus, Prof. Monther A. Khanfar, Dr. Hashem Shorafa, Prof. Steven H. Strauss and Prof. Dr. Konrad Seppelt

      Article first published online: 4 APR 2012 | DOI: 10.1002/chem.201102960

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      The new radicals: The [C6I6]+ radical cation is, in contrast to all other [C6X6]+ radical cations presented herein, not Jahn–Teller distorted.

    21. Peptides

      Synthesis and Conformation of Fluorinated β-Peptidic Compounds (pages 6655–6662)

      Dr. Victoria Peddie, Prof. Raymond J. Butcher, Prof. Ward T. Robinson, Prof. Matthew C. J. Wilce, Dr. Daouda A. K. Traore and Prof. Andrew D. Abell

      Article first published online: 19 APR 2012 | DOI: 10.1002/chem.201200313

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      Making moves: X-ray crystal structures were obtained for a series of α-fluoro-β-amino acids and small fluorinated β-peptides (see picture for an example). When fluorine was positioned α to a carbonyl group, the F[BOND]C[BOND]C[DOUBLE BOND]O moiety was found to adopt an antiperiplanar conformation; but when fluorine was positioned β to an amide nitrogen, a conformation in which C[BOND]F and C[BOND]N(CO) bonds are gauche was favoured.

    22. Logic Gates

      Versatile Logic Devices Based on Programmable DNA-Regulated Silver-Nanocluster Signal Transducers (pages 6663–6669)

      Zhenzhen Huang, Yu Tao, Dr. Fang Pu, Prof. Dr. Jinsong Ren and Prof. Dr. Xiaogang Qu

      Article first published online: 4 APR 2012 | DOI: 10.1002/chem.201103859

      Thumbnail image of graphical abstract

      The DNA after tomorrow: A DNA-encoding strategy for regulating the fluorescence behavior of silver nanoclusters (AgNCs) was developed. The AgNCs were used as signal transducers to construct versatile molecular logic gates and a molecular keypad that was capable of constructing crossword puzzles, whilst simultaneously addressing the concerns of simple and universal design, as well as biocompatible operations.

    23. Ligand Design

      Expanding the Chemistry of Cationic N-Heterocyclic Carbenes: Alternative Synthesis, Reactivity, and Coordination Chemistry (pages 6670–6678)

      Björn Hildebrandt, Dr. Stephan Raub, Prof. Dr. Walter Frank and Prof. Dr. Christian Ganter

      Article first published online: 4 APR 2012 | DOI: 10.1002/chem.201103707

      Thumbnail image of graphical abstract

      Widening our knowledge: The properties and reactions of the cationic N-heterocyclic carbene A are reported (see scheme), including the formation of transition-metal complexes. X-ray structural, electrochemical, and vibrational data indicate that A is an electron-poor carbene. Two additional synthetic approaches to the complexes of ligand A are presented.

    24. Asymmetric Catalysis

      Organocatalytic Asymmetric Conjugate Addition of 3-Monosubstituted Oxindoles to (E)-1,4-Diaryl-2-buten-1,4-diones: A Strategy for the Indirect Enantioselective Furanylation and Pyrrolylation of 3-Alkyloxindoles (pages 6679–6687)

      Yu-Hua Liao , Xiong-Li Liu , Dr. Zhi-Jun Wu, Prof. Xi-Lin Du, Prof. Dr. Xiao-Mei Zhang and Prof. Dr. Wei-Cheng Yuan

      Article first published online: 12 APR 2012 | DOI: 10.1002/chem.201103293

      Thumbnail image of graphical abstract

      It's a cinch! An efficient cinchonine-catalyzed asymmetric conjugate addition of 3-monosubstituted oxindoles to (E)-1,4-diaryl-2-buten-1,4-diones results in 3,3′-disubstituted oxindoles. Cyclization of the 1,4-dicarbonyl moiety in the Michael adducts generates 3-furanyl- or 3-pyrrolyl-3-alkyl-oxindoles under different Paal–Knorr conditions (see scheme).

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      Preview: Chem. Eur. J. 22/2012 (page 6691)

      Article first published online: 15 MAY 2012 | DOI: 10.1002/chem.201290087

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