Chemistry - A European Journal

Cover image for Vol. 18 Issue 47

November 19, 2012

Volume 18, Issue 47

Pages 14877–15206

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Communications
    8. Full Papers
    1. You have free access to this content
      Cover Picture: Synthesis and Characterization of Pd@MxCu1−x (M=Au, Pd, and Pt) Nanocages with Porous Walls and a Yolk–Shell Structure through Galvanic Replacement Reactions (Chem. Eur. J. 47/2012) (page 14877)

      Shuifen Xie, Prof. Mingshang Jin, Dr. Jing Tao, Dr. Yucai Wang, Prof. Zhaoxiong Xie, Dr. Yimei Zhu and Prof. Younan Xia

      Article first published online: 13 NOV 2012 | DOI: 10.1002/chem.201290201

      Thumbnail image of graphical abstract

      Pd@MxCu1−x (M=Au, Pd, Pt) nanocageswith porous alloy walls and a yolk–shell structure were prepared by using a galvanic replacement reaction that involved Pd@Cu core–shell nanocubes and noble-metal-salt precursors in ethylene glycol. As a substitute of the conventional sacrificial templates of Ag, the Cu-based nanostructures can reduce the cost and provide more driving force for the galvanic replacement. For more details see the Full Paper by Y. Xia et al. on page 14974 ff.

  2. Editorial

    1. Top of page
    2. Cover Picture
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Communications
    8. Full Papers
    1. European Young Chemist Award 2012

      You have free access to this content
  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Communications
    8. Full Papers
    1. Graphical Abstract: Chem. Eur. J. 47/2012 (pages 14887–14897)

      Article first published online: 13 NOV 2012 | DOI: 10.1002/chem.201290202

  4. News

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

    1. Top of page
    2. Cover Picture
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Communications
    8. Full Papers
    1. Fluorinated Cyclopropanes

      Syntheses and Applications of Monofluorinated Cyclopropanes (pages 14904–14917)

      Dr. Emilie David, Gaëlle Milanole, Pavel Ivashkin, Dr. Samuel Couve-Bonnaire, Prof. Dr. Philippe Jubault and Prof. Dr. Xavier Pannecoucke

      Article first published online: 29 OCT 2012 | DOI: 10.1002/chem.201202831

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      The combination of a fluorine atom and a cyclopropane ring, which both possess unique structural and chemical features, can generate new relevant building blocks for the discovery of efficient fluorinated biologically active agents. In this review, the different strategies to access monofluorocyclopropanes are discussed and some of their attractive biological applications are highlighted (see scheme; MIRC= Michael initiated ring closure).

  6. Communications

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

      Cobalt(II)-Catalyzed 1,4-Addition of Organoboronic Acids to Activated Alkenes: An Application to Highly cis-Stereoselective Synthesis of Aminoindane Carboxylic Acid Derivatives (pages 14918–14922)

      Min-Hsien Chen, Dr. Subramaniyan Mannathan, Dr. Pao-Shun Lin and Prof. Dr. Chien-Hong Cheng

      Article first published online: 30 OCT 2012 | DOI: 10.1002/chem.201202575

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      It all adds up: The 1,4-addition of organoboronic acids to activated alkenes catalyzed by [Co(dppe)Cl2] is described. A [3+2]-annulation reaction of ortho-iminoarylboronic acids with acrylates to give various aminoindane carboxylic acid derivatives with cis-stereoselectivity is also demonstrated (see scheme; dppe=1,2-bis(diphenylphosphino)ethane).

    2. Transmetalation

      The Fluoride-Free Transmetalation of Organosilanes to Gold (pages 14923–14928)

      Stéphanie Dupuy, Prof. Dr. Alexandra M. Z. Slawin and Prof. Dr. Steven P. Nolan

      Article first published online: 12 OCT 2012 | DOI: 10.1002/chem.201202299

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      Golden transfer: The versatile gold(I) complex [Au(IPr)(OH)] permits very straightforward access to a series of aryl-, vinyl- and alkylgold silanolates by reaction with the appropriate silane reagent. These silanolate compounds are key intermediates in a fluoride-free process that results in the net transmetalation of organosilanes to gold.

    3. Cascade Reactions

      Highly Enantio- and Diastereoselective Generation of Two Quaternary Centers in Spirocyclopropanation of Oxindole Derivatives. (pages 14929–14933)

      Artur Noole, Natalia S. Sucman, Dr. Mikhail A. Kabeshov, Prof. Dr. Tõnis Kanger, Prof. Dr. Fliur Z. Macaev and Prof. Dr. Andrei V. Malkov

      Article first published online: 30 OCT 2012 | DOI: 10.1002/chem.201203099

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      Spirocyclopropanes: Only one out of eight possible stereoisomers was obtained in the asymmetric cascade cyclopropanation of alkylidene oxindoles with ethyl 2-chloroacetoacetate. Improved catalyst design ensured that spirocyclopropyl oxindoles featuring two quaternary centers were synthesized in high yield and high enantio- and diastereoselectivity (see scheme).

    4. Tandem Reactions

      Orthogonal C[BOND]N Plus C[BOND]C Tandem Reaction of Iodoanilines Leading to Styrylguanidines Catalyzed by Supported Palladium Nanoparticles (pages 14934–14938)

      Dr. Abdessamad Grirrane, Prof. Dr. Hermenegildo Garcia, Prof. Dr. Avelino Corma and Dr. Eleuterio Álvarez

      Article first published online: 15 OCT 2012 | DOI: 10.1002/chem.201202823

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      Two birds, one nanoparticle: A highly efficient and selective tandem reaction comprising C[BOND]N and C[BOND]C cross-coupling of iodoanilines to form styrylguanidines by using a recyclable, heterogeneous, supported palladium nanoparticle catalyst is reported (see scheme). A mechanistic proposal based on coordination of palladium nanoparticles to the basic N atoms of aniline and guanidine is supported by isolation of palladium complexes with aniline or guanidine.

    5. Molecular Devices

      A DNA-Based and Electrochemically Transduced Keypad Lock System with Reset Function (pages 14939–14942)

      Wei Hong, Dr. Yan Du, Tianshu Wang, Jiyang Liu, Dr. Yaqing Liu, Prof. Jin Wang and Prof. Erkang Wang

      Article first published online: 25 OCT 2012 | DOI: 10.1002/chem.201203286

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      Try your lock: A resettable DNA-based keypad lock system with electrochemical current as output signal has been successfully developed as proof of concept (see scheme). The system is triggered to ON only when the inputs are adopted with an appropriate combination and exact sequence. The reset function can be facilely realized.

    6. Synthetic Methods

      Efficient Synthesis and First Regioselective C-3 Direct Arylation of Imidazo[1,2-b]pyrazoles (pages 14943–14947)

      Sandrine Grosse, Dr. Christelle Pillard, Dr. Stéphane Massip, Prof. Jean Michel Léger, Prof. Christian Jarry, Dr. Stéphane Bourg, Dr. Philippe Bernard and Prof. Gérald Guillaumet

      Article first published online: 19 OCT 2012 | DOI: 10.1002/chem.201202593

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      Highly regioselective: An efficient synthesis of the imidazo[1,2-b]pyrazole core has been developed, and the first regioselective palladium-catalyzed direct arylation of the C-3 position is described (see scheme). Good to excellent yields were obtained for a wide range of aryl partners with electron-rich and electron-poor substituents. This methodology allows rapid access to a large variety of imidazo[1,2-b]pyrazole products and could open the way to the design of new biologically active compounds.

    7. Raman Scattering

      Galvanic-Cell-Induced Growth of Ag Nanosheet-Assembled Structures as Sensitive and Reproducible SERS Substrates (pages 14948–14953)

      Dr. Zhongbo Li, Prof. Guowen Meng, Prof. Qing Huang, Dr. Chuhong Zhu, Dr. Zhuo Zhang and Dr. Xiangdong Li

      Article first published online: 18 OCT 2012 | DOI: 10.1002/chem.201201690

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      SERS up: Ag nanosheet-assembled structures with controlled morphologies were achieved on indium tin oxide substrates by galvanic-cell-induced growth (see figure). These structures exhibit a highly active and homogeneous surface-enhanced Raman scattering (SERS) effect, and show promising potential as reliable SERS substrates for detection of trace polychlorinated biphenyls.

    8. Self-Assembly

      Supramolecular Gel-Assisted Formation of Fullerene Nanorods (pages 14954–14956)

      Dr. Chun Zhang, Jing Wang, Jing-Jing Wang, Min Li, Prof. Xiang-Liang Yang and Prof. Hui-Bi Xu

      Article first published online: 30 OCT 2012 | DOI: 10.1002/chem.201202721

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      Gel it like it is: Fullerene nanorods (see figure) with a length of several micrometers, can be easily synthesized by a supramolecular gel-assisted self-assembly method (SGAS). The results presented here may be useful for the design and construction of new organic nanomaterials by SGAS.

    9. Alternated Stacks of Nonpolar Oligo(p-phenyleneethynylene)-BODIPY Systems (pages 14957–14961)

      Alexander Florian, Dr. María José Mayoral, Dr. Vladimir Stepanenko and Dr. Gustavo Fernández

      Article first published online: 23 OCT 2012 | DOI: 10.1002/chem.201203279

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      Supramolecular chemistry: The self-assembly of an oligo(p-phenyleneethynylene)–4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (OPE–BODIPY) system into alternated 1D π stacks in solution exhibited liquid-crystalline properties at room temperature. This system represents a new approach towards a controlled dye organization exclusively driven by π–π interactions (see figure).

    10. Supported Catalysts

      Improved Selectivity by Stabilizing and Exposing Active Phases on Supported Pd Nanoparticles in Acetylene-Selective Hydrogenation (pages 14962–14966)

      Dr. Lidong Shao, Dr. Bingsen Zhang, Dr. Wei Zhang, Dr. Detre Teschner, Dr. Frank Girgsdies, Prof. Dr. Robert Schlögl and Dr. Dang Sheng Su

      Article first published online: 22 OCT 2012 | DOI: 10.1002/chem.201202608

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      Palladium dynamics: Under hydrogenation conditions, saturating over-active palladium by carbon diffusion leads to a stable and selective particle surface. By choosing supports with suitable geometric structures and establishing a strong interaction between supports and metal particles, accumulated species can be regularly rearranged and reaction-selective phases can be exposed (see figure).

  7. Full Papers

    1. Top of page
    2. Cover Picture
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Minireview
    7. Communications
    8. Full Papers
    1. Molecular Imprinting

      Multilayer Films with Nanocontainers: Redox-Controlled Reversible Encapsulation of Guest Molecules (pages 14968–14973)

      Jiawei Zhang, Yiliu Liu, Bin Yuan, Prof. Zhiqiang Wang, Prof. Monika Schönhoff and Prof. Xi Zhang

      Article first published online: 30 OCT 2012 | DOI: 10.1002/chem.201202978

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      Chemical containers: The fabrication of stable surface-imprinted multilayer films with cucurbit[8]uril (CB[8]) is demonstrated. The as-prepared multilayer films exhibit good properties as surface-imprinted multilayers, because CB[8] molecules that are locked inside the multilayers can act as nanocontainers with specific binding to certain guest molecules, and the loading and release of the guest is redox controllable and reversible (see figure).

    2. Nanocages

      Synthesis and Characterization of Pd@MxCu1−x (M=Au, Pd, and Pt) Nanocages with Porous Walls and a Yolk–Shell Structure through Galvanic Replacement Reactions (pages 14974–14980)

      Shuifen Xie, Prof. Mingshang Jin, Dr. Jing Tao, Dr. Yucai Wang, Prof. Zhaoxiong Xie, Dr. Yimei Zhu and Prof. Younan Xia

      Article first published online: 29 OCT 2012 | DOI: 10.1002/chem.201202477

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      Breaking the egg! Pd@MxCu1−x (M=Au, Pd, and Pt) nanocages with porous walls and a yolk–shell nanostructure were synthesized through a facile galvanic replacement reaction between noble-metal-salt precursors and Pd@Cu core–shell cubic templates (see figure).

    3. Biomimetic Oxidation

      A Biomimetic Pathway for Vanadium-Catalyzed Aerobic Oxidation of Alcohols: Evidence for a Base-Assisted Dehydrogenation Mechanism (pages 14981–14988)

      Bethany N. Wigington, Dr. Michael L. Drummond, Prof. Dr. Thomas R. Cundari, Dr. David L. Thorn, Dr. Susan K. Hanson and Prof. Dr. Susannah L. Scott

      Article first published online: 18 OCT 2012 | DOI: 10.1002/chem.201202499

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      Biomimetic aerobic oxidation of alcohols, as catalyzed by an (8-hydroxyquinolinato)vanadium complex, is promoted by Brønsted bases, which deprotonate the alcoholato ligand and thereby induce electronic reorganization (see scheme). This base-assisted dehydrogenation resembles certain metalloenzyme-catalyzed oxidations, in which a base situated near the active site participates directly in the redox reaction.

    4. Ultrafast Structure Elucidation

      Two-Dimensional Infrared Spectroscopy Reveals the Structure of an Evans Auxiliary Derivative and Its SnCl4 Lewis Acid Complex (pages 14989–14995)

      Andreas T. Messmer, Katharina M. Lippert, Sabrina Steinwand, Dr. Eliza-Beth W. Lerch, Kira Hof, David Ley, Dr. Dennis Gerbig, Dr. Heike Hausmann, Prof. Dr. Peter R. Schreiner and Prof. Dr. Jens Bredenbeck

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201201583

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      Structure seen from a vibrational angle: Ultrafast polarization-dependent 2D-IR spectroscopy is shown to be an excellent complement to common methods for investigating short-lived reactive species. By measuring angles between vibrational transition dipole moments, the conformation of a Diels–Alder dienophile and the conformational change induced by formation of a substrate–catalyst complex in fast dynamic equilibrium is definitively resolved (see figure).

    5. Chemical Vapor Deposition

      Synthesis, Characterization, Electronic and Gas-Sensing Properties towards H2 and CO of Transparent, Large-Area, Low-Layer Graphene (pages 14996–15003)

      Emine Kayhan, Ravi Mohan Prasad, Dr. Alexander Gurlo, Dr. Oktay Yilmazoglu, Dr. Jörg Engstler, Dr. Emanuel Ionescu, Songhak Yoon, Prof. Dr. Anke Weidenkaff and Prof. Dr. Jörg J. Schneider

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201201880

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      Graphene sensor: Low-layered graphene is accessible by chemical vapor deposition followed by detachment from the substrate by an acid etch. Graphene can be transferred onto various substrates allowing studies of its chemical sensor activity towards H2 and CO. The picture shows a 1×1 cm−1 graphene piece after detaching from the substrate. TEM depicts a high degree of order in graphene and gas-sensing results show a high sensitivity towards H2 gas (see figure).

    6. Total Synthesis

      The Plakotenins: Biomimetic Diels–Alder Reactions, Total Synthesis, Structural Investigations, and Chemical Biology (pages 15004–15020)

      Dr. Emmanuel Bourcet, Larissa Kaufmann, Dr. Stephanie Arzt, Dr. Angela Bihlmeier, Prof. Dr. Wim Klopper, Dr. Ute Schepers and Prof. Dr. Stefan Bräse

      Article first published online: 4 OCT 2012 | DOI: 10.1002/chem.201201585

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      Plakotenins—the full family: The total syntheses of plakotenin, iso-plakotenin, nor-plakotenin, and homo-plakotenin have been described using a “late-stage” biomimetic ring closure and an “early-stage” Diels–Alder reaction with subsequent modification (see scheme). Biological tests were investigated showing that the stereochemistry was an important aspect for cytotoxicity.

    7. Enzyme Catalysis

      Striking Improvement in Peroxidase Activity of Cytochrome c by Modulating Hydrophobicity of Surface-Functionalized Gold Nanoparticles within Cationic Reverse Micelles (pages 15021–15030)

      Subhabrata Maiti, Krishnendu Das, Sounak Dutta and Prof. Prasanta Kumar Das

      Article first published online: 27 SEP 2012 | DOI: 10.1002/chem.201202398

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      Congestion charge: The peroxidase activity of cytochrome c remarkably improved in the presence of surface-functionalized gold nanoparticles (GNPs; capped with amphiphiles) within cetyltrimethylammonium bromide (CTAB) reverse micelles (see figure). Cytochrome c located at the congested interface lost its tertiary structure due to hydrophobic crowding in the vicinity of it by the GNP-capping amphiphiles. Consequently, the exposed inner heme core of the protein had greater interaction with the substrate, which resulted in higher peroxidase activity.

    8. Density Functional Theory

      Synthesis of Amino, Azido, Nitro, and Nitrogen-Rich Azole-Substituted Derivatives of 1H-Benzotriazole for High-Energy Materials Applications (pages 15031–15037)

      Dharavath Srinivas, Vikas D. Ghule, Prof. Surya P. Tewari and Dr. Krishnamurthi Muralidharan

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201202481

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      Energetic materials: Computed electrostatic potential on 0.001 au molecular surfaces of the benzotriazole-based energetic compound shown in the graphic (color ranges, in kcal mol−1, red: greater than 15.74, yellow: between 15.74 and 13.82, green: between 13.82 and 11.91, blue: negative).

    9. Polymorphic Crystals

      Crystal Structures and Emitting Properties of Trifluoromethylaminoquinoline Derivatives: Thermal Single-Crystal-to-Single-Crystal Transformation of Polymorphic Crystals That Emit Different Colors (pages 15038–15048)

      Yuichiro Abe, Dr. Satoru Karasawa and Dr. Noboru Koga

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201201213

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      Singles club: 2,4-Trifluoromethylquinolines with amine, methylamine, phenylamine, and dimethylamine substituents were prepared and their solid-state emitting properties were investigated. The emitting color changes with thermal single-crystal-to-single-crystal transformation between the polymorphic crystals were observed in the single crystals of the methylamine (shown) and phenylamine derivatives.

    10. Mesoporous Materials

      Foamlike Porous Spinel MnxCo3−xO4 Material Derived from Mn3[Co(CN)6]2nH2O Nanocubes: A Highly Efficient Anode Material for Lithium Batteries (pages 15049–15056)

      Lin Hu, Ping Zhang, Hao Zhong, Xinrui Zheng, Nan Yan and Prof. Qianwang Chen

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201200412

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      The cube root: Porous spinel MnxCo3−xO4 nanocubes are derived from Mn3[Co(CN)6]2nH2O. The as-prepared nanocubes display excellent Li-ion battery performance with good cycle life and high capacity (733 mAh g−1 is maintained after 30 cycles) due to a foamlike porous inner architecture (see figure). Anode systems based primarily on manganese are proposed.

    11. Phase Separation

      Influence of the Solvent and the Enantiomeric Purity on the Transition between Different Supramolecular Polymers (pages 15057–15064)

      Dr. Martin Wolffs, Juliën L. J. van Velthoven, Dr. Xianwen Lou, Ralf A. A. Bovee, Maarten Pouderoijen, Joost L. J. van Dongen, Dr. Albertus P. H. J. Schenning and Prof. Dr. E. W. Meijer

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201200984

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      Phase separation in supramolecular assemblies: The use of star-shaped oligo(p-phenylene vinylene) (OPV) derivatives with 24 stereocenters allowed the design of a system in which the high mismatch penalty between the enantiomers results in demixing in the self-assembled state. Furthermore, a transition between different self-assembled structures has been observed, in which the rate of the transition has been found to depend both on the solvent and the enantiomeric purity (see figure).

    12. Polymer Nanofibers

      Dynamically Controllable Emission of Polymer Nanofibers: Electrofluorescence Chromism and Polarized Emission of Polycarbazole Derivatives (pages 15065–15072)

      Kohsuke Kawabata and Prof. Hiromasa Goto

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201201471

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      Emission control: Electrochemical polymerization of N-alkyl-2,7-di(2-thienyl)carbazoles produced fluorescent conjugated polymer films, some of which showed nanofiber formation on their surface. The polymer nanofibers were stacked on a substrate electrode (see figure). The fluorescence intensity of the nanofiber films was controllable with application of voltage.

    13. Ion-Pair Receptors

      Calix[4]pyrrole-Based Heteroditopic Ion-Pair Receptor That Displays Anion-Modulated, Cation-Binding Behavior (pages 15073–15078)

      In-Won Park, Dr. Jaeduk Yoo, Dr. Suman Adhikari, Jung Su Park, Prof. Jonathan L. Sessler and Prof. Chang-Hee Lee

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201202777

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      Anion modulates the cation binding: A new ditopic calix[4]pyrrole-based ion-pair receptor that binds halide ions to form stable complexes was synthesized. Treatment of the halide-ion complexes with Group I and II metal ions revealed unique interactions that were found to depend on both the choice of the added cation and the precomplexed anion (see figure).

    14. Insertion

      M4(CH2)4 Cubane-Type Rare-Earth Methylidene Complexes: Unique Reactivity toward Unsaturated C[BOND]O, C[BOND]N, and C[BOND]S Bonds (pages 15079–15085)

      Tingting Li, Dr. Masayoshi Nishiura, Dr. Jianhua Cheng, Prof. Dr. Yang Li and Prof. Dr. Zhaomin Hou

      Article first published online: 11 OCT 2012 | DOI: 10.1002/chem.201202796

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      The tetranuclear lutetium methylidene complex [(C5Me4SiMe3)Lu(μ3-CH2)]4 showed diverse reactivity toward various substrates. Its reactions with carbon monoxide, iPrN[DOUBLE BOND]C[DOUBLE BOND]NiPr, PhNCS, and PhNCO gave the corresponding structurally characterized ketene dianion, ethylene diamido, ethylene amido thiolate, and malonodiimidate complexes, respectively (see scheme).

    15. Cluster Compounds

      3 D MOFs Containing Trigonal Bipyramidal Ln5 Clusters as Nodes: Large Magnetocaloric Effect and Slow Magnetic Relaxation Behavior (pages 15086–15091)

      Peng-Fei Shi, Prof. Dr. Yan-Zhen Zheng, Dr. Xiao-Qing Zhao, Gang Xiong, Prof. Dr. Bin Zhao, Fan-Fan Wan and Prof. Dr. Peng Cheng

      Article first published online: 18 OCT 2012 | DOI: 10.1002/chem.201202412

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      Two 3D heterometal–organic frameworks based on infrequent, trigonal bipyramidal geometry, Ln5 clusters as nodes were structurally and magnetically characterized (Ln=Gd and Dy). The results indicate a large magnetocaloric effect of up to 30.7 J kg−1 K−1 for Ln=Gd and slow magnetic relaxation for Ln=Dy (see figure).

    16. Porphyrines

      Synthesis and Self-Organization of Zinc β-(Dialkoxyphosphoryl)porphyrins in the Solid State and in Solution (pages 15092–15104)

      Ekaterina V. Vinogradova, Dr. Yulia Y. Enakieva, Prof. Sergey E. Nefedov, Dr. Kirill P. Birin, Prof. Aslan Y. Tsivadze, Prof. Yulia G. Gorbunova, Dr. Alla G. Bessmertnykh Lemeune, Dr. Christine Stern and Prof. Roger Guilard

      Article first published online: 5 OCT 2012 | DOI: 10.1002/chem.201202596

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      Metal-mediated C[BOND]P bond-forming reactions were successfully applied to the synthesis of β-(dialkoxyphosphoryl)porphyrins for the first time. An unusual one-pot sequence involving consecutive reduction and phosphorylation of H2TPPBr4 (TPP=tetraphenylporphyrin) led to the formation of bis(dialkoxy)phosphorylporphyrins in good yields (see figure). According to X-ray studies, the zinc β-phosphorylporphyrinate complexes exist as cofacial dimers in the solid state.

    17. Metal–Metal bonds

      Synthesis, Structure, and Reactivity of a Dimeric Zinc(I) Compound Stabilized by a Sterically Demanding Diiminophosphinate Ligand (pages 15105–15112)

      Dr. Andreas Stasch

      Article first published online: 5 OCT 2012 | DOI: 10.1002/chem.201202560

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      Think zinc: The synthesis of a new sterically demanding diiminophosphinate ligand and a series of heteroleptic zinc(II) complexes is reported. Reductions of zinc(II) halide complexes with a dimeric magnesium(I) compound afforded a new dimeric zinc(I) compound in good yield. Reactions of the zinc(I) dimer have been carried out and the oxidative addition of small alkyl halides has been observed and found to form both zinc alkyl and zinc halide complexes (see figure).

    18. Divergent Reactions

      Gold(I)-Catalyzed Regiodivergent Rearrangements: 1,2- and 1,2′-Alkyl Migration in Skipped Alkynyl Ketones (pages 15113–15121)

      Wenbo Li, Yuying Li, Dr. Guanghua Zhou, Xiangshu Wu and Prof. Dr. Junliang Zhang

      Article first published online: 5 OCT 2012 | DOI: 10.1002/chem.201201727

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      Skeleton crew: A gold-catalyzed regiodivergent rearrangement of 2-alkynyl carbonyl compounds was developed for the synthesis of dihydrobenzofuran and dihydroisobenzofuran skeletons (see scheme). The 1,2-alkyl migration reaction includes a concerted process and the 1,2′-alkyl migration reaction proceeds through a tandem cyclization/C[BOND]C bond cleavage/C[BOND]Au bond substitution sequence.

    19. Graphene

      Hemin-Functionalized Reduced Graphene Oxide Nanosheets Reveal Peroxynitrite Reduction and Isomerization Activity (pages 15122–15132)

      Amit A. Vernekar and Prof. Dr. Govindasamy Mugesh

      Article first published online: 5 OCT 2012 | DOI: 10.1002/chem.201202272

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      Reduced graphene oxide–hemin hybrid nanosheets exhibit a remarkable peroxynitrite isomerase and reductase activity under physiologically relevant conditions. The electronic communication between graphene and hemin provides the required synergistic effect for an efficient isomerization of peroxynitrite to nitrate. The increase in the local concentration of nitrite due to the presence of graphene layers facilitates the recombination of FeIV=O and nitrite in the catalytic cycle (see figure).

    20. DNA

      A Tri-copper(II) Complex Displaying DNA-Cleaving Properties and Antiproliferative Activity against Cancer Cells (pages 15133–15141)

      Dr. Kogularamanan Suntharalingam, Douglas J. Hunt, Dr. Alexandra A. Duarte, Dr. Andrew J. P. White, Dr. David J. Mann and Prof. Ramon Vilar

      Article first published online: 11 OCT 2012 | DOI: 10.1002/chem.201202482

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      Terpyridine ligands: A new tri-copper(II) complex has been prepared and shown to cleave DNA efficiently without the need for external co-reductants. The complex displayed a high cytotoxic effect against several cancer-cell lines including the cisplatin-resistant MOLT-4 leukaemia-cell line (see figure). The complex is cell permeable and a proportion of it localises in the nucleus. Cellular studies demonstrated that this complex induces DNA damage in the cell.

    21. Photochemistry

      DNA Sequence and Ancillary Ligand Modulate the Biexponential Emission Decay of Intercalated [Ru(L)2dppz]2+ Enantiomers (pages 15142–15150)

      Dr. Andrew W. McKinley, Dr. Johanna Andersson, Dr. Per Lincoln and Dr. Eimer M. Tuite

      Article first published online: 5 OCT 2012 | DOI: 10.1002/chem.201201279

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      Controlling the light switch: The bi-exponential emission decay parameters (τi and αi) of [Ru(L)2dppz]2+ (L=phenanthroline or bipyridine, dppz=dipyrido[3,2-a:2′,3′-c]phenazine) depend on polynucleotide sequence, enantiomer, and the nature of L. Differential water exposure in two intercalated geometries from the minor groove give rise to the bi-exponential decays. Guanosine quenches [Ru(phen)2dppz]2+ emission, producing shorter lifetimes (see figures).

    22. Oxidative Cyclization

      Palladium(II)-Catalyzed Oxidative Cyclization of Allylic Tosylcarbamates: Scope, Derivatization, and Mechanistic Aspects (pages 15151–15157)

      Dr. Antoine Joosten, Dr. Andreas K. Å. Persson, Dr. Renaud Millet, Magnus T. Johnson and Prof. Jan-E. Bäckvall

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201202359

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      A highly efficient oxidative cyclization of allylic tosylcarbamates occurs through a palladium-catalyzed trans-amidopalladation–β-hydride elimination sequence to give vinyloxazolidinones in good to high yields (see scheme; Ts=tosyl, BQ=benzoquinone). The oxazolidinone products are important synthetic intermediates that can be transformed to a range of functionalized products.

    23. Photochemistry

      Direct C[BOND]H Functionalization of Enamides and Enecarbamates by Using Visible-Light Photoredox Catalysis (pages 15158–15166)

      Heng Jiang, Chengmei Huang, Jiajia Guo, Chuanqi Zeng, Prof. Dr. Yan Zhang and Prof. Dr. Shouyun Yu

      Article first published online: 27 SEP 2012 | DOI: 10.1002/chem.201201716

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      Lighting the way! A mild, practical, and environmentally friendly strategy for alkylation, trifluoromethylation, and arylation of enamides and enecarbamates with a broad substrate scope by using visible-light photoredox-catalyzed direct C[BOND]H functionalization is described (see scheme).

    24. Biosensors

      Theoretical Assessment of Binding and Mass-Transport Effects in Electrochemical Affinity Biosensors That Utilize Nanoparticle Labels for Signal Amplification (pages 15167–15177)

      Dr. Jie Zhang, Boon Ping Ting and Prof. Dr. Jackie Y. Ying

      Article first published online: 27 SEP 2012 | DOI: 10.1002/chem.201201384

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      Mis-matchmaker: A significant mismatch between the calibration curve and adsorption isotherm can occur when mass transport plays an important role in electrochemical signal amplification (see figure). This can lead to a dramatic interference of nonspecific adsorption of labels in the measurements.

    25. Cyclometalation

      Cycloruthenated Complexes from Imine-Based Heterocycles: Synthesis, Characterization, and Reactivity toward Alkynes (pages 15178–15189)

      Dr. Luciano Cuesta, Dr. Tatiana Soler and Dr. Esteban P. Urriolabeitia

      Article first published online: 27 SEP 2012 | DOI: 10.1002/chem.201201382

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      Building fused bis-heterocycles! In a new approach to the synthesis of highly valuable fused bis-heteroarenes, acetylenes are inserted into the Ru[BOND]C bond of cyclometalated heterocyclic complexes with an imine as a directing group. This very general method allows the “fusion” of a pyridinium ring to thiophene, furan, pyrrole, and the corresponding benzoannulated derivatives (see scheme). A novel family of organometallic intermediates, which displays an unexpected structure as a result of metal–ligand cooperation, was identified.

    26. Chiral Salts

      A Highly Stereoselective Synthesis of Glycidic Amides Based on a New Class of Chiral Sulfonium Salts: Applications in Asymmetric Synthesis (pages 15190–15201)

      Prof. Dr. Francisco Sarabia, Carlos Vivar-García, Dr. Miguel García-Castro, Cristina García-Ruiz, Francisca Martín-Gálvez, Dr. Antonio Sánchez-Ruiz and Dr. Samy Chammaa

      Article first published online: 18 OCT 2012 | DOI: 10.1002/chem.201201332

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      Salty but sweet: Chiral sulfonium salts that featured a bicyclic system reacted with carbonyl compounds to afford epoxy amides with excellent stereoselectivity. A wide array of 1,2-functionalized systems was prepared by oxirane-ring-opening reactions (see scheme).

    27. Total Synthesis

      Formal Total Synthesis of Palmerolide A (pages 15202–15206)

      Dr. Amit B. Pawar and Prof. Dr. Kavirayani R. Prasad

      Article first published online: 2 OCT 2012 | DOI: 10.1002/chem.201202324

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      Assembled from abundance: A formal total synthesis of the 20-membered marine macrolide, palmerolide A, from tartaric acid is described (see scheme). Key features of the synthesis include the application of Boord olefination and ring-closing metathesis.

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