Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 21

May 19, 2014

Volume 53, Issue 21

Pages 5217–5471

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Addendum
    6. Corrigenda
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlight
    12. Minireview
    13. Review
    14. Communications
    1. You have free access to this content
      Cover Picture: Silver(I)-Catalyzed Hydroazidation of Ethynyl Carbinols: Synthesis of 2-Azidoallyl Alcohols (Angew. Chem. Int. Ed. 21/2014) (page 5217)

      Zhenhua Liu, Jianquan Liu, Lin Zhang, Dr. Peiqiu Liao, Prof. Jinna Song and Prof. Xihe Bi

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201401134

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      The hydroazidation of unactivated alkynes is described by X. Bi and co-workers in their Communication on page 5305 ff. Silver catalysis enabled the chemo- and regioselective transformation of ethynyl carbinols into vinyl azides. A wide variety of 2-azidoallyl alcohols were obtained in good to excellent yields. The synthetic utility of 2-azidoallyl alcohols was demonstrated by further transformations into NH aziridines.

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      Inside Cover: The Origin of the Selectivity and Activity of Ruthenium-Cluster Catalysts for Fuel-Cell Feed-Gas Purification: A Gas-Phase Approach (Angew. Chem. Int. Ed. 21/2014) (page 5218)

      Dr. Sandra M. Lang, Prof. Dr. Thorsten M. Bernhardt, Marjan Krstić and Prof. Dr. Vlasta Bonačić-Koutecký

      Version of Record online: 14 MAY 2014 | DOI: 10.1002/anie.201401131

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      Hydrogen feed gases generated by reformation of fossil fuels contain minute quantities of CO. For use in fuel cells the CO must be removed selectively to prevent fuel-cell-catalyst poisoning. T. M. Bernhardt, V. Bonačić-Koutecký, and co-workers show in their Communication on page 5467 ff. that sub-nanometer ruthenium clusters are highly effective at doing so by converting CO into benign CH4. Ion-trap mass spectrometry and DFT calculations identify the properties of these clusters responsible for their selectivity and activity.

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      Inside Back Cover: Evidence for Extensive Single-Electron-Transfer Chemistry in Boryl Anions: Isolation and Reactivity of a Neutral Borole Radical (Angew. Chem. Int. Ed. 21/2014) (page 5473)

      Dr. Rüdiger Bertermann, Prof. Dr. Holger Braunschweig, Dr. Rian D. Dewhurst, Dipl.-Chem. Christian Hörl, Dipl.-Chem. Thomas Kramer and Dr. Ivo Krummenacher

      Version of Record online: 16 APR 2014 | DOI: 10.1002/anie.201403558

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      The isolation of a neutral borole radical is described for the first time by H. Braunschweig et al. in their Communication on page 5453 ff. What appears at first to be boron-centered nucleophilicity was shown to be single-electron-transfer (SET; i.e. radical) reactivity when a neutral borole radical is isolated both as a final product and as an intermediate in the reaction of borole anions with triorganyl halides of tin and lead.

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      Back Cover: Large Zero-Field Splittings of the Ground Spin State Arising from Antisymmetric Exchange Effects in Heterometallic Triangles (Angew. Chem. Int. Ed. 21/2014) (page 5474)

      Samantha A. Magee, Dr. Stephen Sproules, Dr. Anne-Laure Barra, Dr. Grigore A. Timco, Nicholas F. Chilton, Prof. David Collison, Prof. Richard E. P. Winpenny and Prof. Eric J. L. McInnes

      Version of Record online: 15 APR 2014 | DOI: 10.1002/anie.201401141

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      The antisymmetric component of the electronic exchange interaction (also known as Dzyaloshinski–Moriya exchange) is often overlooked in modeling the magnetic data of molecular species, but in the Communication by E. J. L. McInnes and co-workers on page 5310 ff., it is shown to be responsible for the large magnetic anisotropy in the S=5/2 ground state of a trimetallic complex. The illustration plays on the concept of “antisymmetry” and triangles with an Escher triangle.

  2. Frontispiece

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    4. Graphical Abstract
    5. Addendum
    6. Corrigenda
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    10. Book Review
    11. Highlight
    12. Minireview
    13. Review
    14. Communications
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      Frontispiece: Heterolytic Cleavage of Hydrogen by an Iron Hydrogenase Model: An Fe-H⋅⋅⋅H-N Dihydrogen Bond Characterized by Neutron Diffraction

      Dr. Tianbiao Liu, Dr. Xiaoping Wang, Dr. Christina Hoffmann, Dr. Daniel L. DuBois and Dr. R. Morris Bullock

      Version of Record online: 14 MAY 2014 | DOI: 10.1002/anie.201482171

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      A synthetic model complex of an iron hydrogenase was used by Bullock et al. on page 5300 ff. to investigate the heterolytic cleavage of H2 using neutron diffraction.

  3. Graphical Abstract

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    5. Addendum
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  4. Addendum

    1. Top of page
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      Addendum: Metal–Organic Organopolymeric Hybrid Framework by Reversible [2+2] Cycloaddition Reaction (page 5232)

      In-Hyeok Park, Anjana Chanthapally, Dr. Zhenjie Zhang, Prof. Dr. Shim Sung Lee, Prof. Dr. Michael J. Zaworotko and Prof. Dr. Jagadese J. Vittal

      Version of Record online: 14 MAY 2014 | DOI: 10.1002/anie.201402066

      This article corrects:

      Metal–Organic Organopolymeric Hybrid Framework by Reversible [2+2] Cycloaddition Reaction1

      Vol. 53, Issue 2, 414–419, Version of Record online: 11 DEC 2013

  5. Corrigenda

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      Corrigendum: Iodine–Iodine Bonding makes Tetra(diiodine)chloride, [Cl(I2)4], Planar (page 5233)

      Dr. Christine Walbaum, M. Sc. Mark Richter, Dipl.-Chem. Ulf Sachs, Dr. Ingo Pantenburg, Prof. Dr. Sebastian Riedel, Prof. Dr. Anja-Verena Mudring and Prof. Dr. Gerd Meyer

      Version of Record online: 14 MAY 2014 | DOI: 10.1002/anie.201402660

      This article corrects:

      Iodine–Iodine Bonding makes Tetra(diiodine)chloride, [Cl(I2)4], Planar1

      Vol. 52, Issue 48, 12732–12735, Version of Record online: 2 OCT 2013

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      Corrigendum: Graphene Oxide Nanoribbons from the Oxidative Opening of Carbon Nanotubes Retain Electrochemically Active Metallic Impurities (page 5233)

      Colin Hong An Wong, Chun Kiang Chua, Bahareh Khezri, Richard D. Webster and Prof. Martin Pumera

      Version of Record online: 14 MAY 2014 | DOI: 10.1002/anie.201403628

      This article corrects:
  6. News

    1. Top of page
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    13. Review
    14. Communications
  7. Author Profile

    1. Top of page
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    14. Communications
    1. Dongho Kim (page 5240)

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201311143

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      “In a spare hour, I go hiking in the forest and mountains. If I could be a piece of lab equipment, I would be a very stable and tunable femtosecond laser …” This and more about Dongho Kim can be found on page 5240.

  8. News

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    14. Communications
  9. Book Review

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    14. Communications
    1. Lithium Batteries. Advanced Technologies and Applications. Edited by Bruno Scrosati, K. M. Abraham, Walter van Schalkwijk and Jusef Hassoun. (page 5242)

      Miran Gaberšček

      Version of Record online: 11 APR 2014 | DOI: 10.1002/anie.201400965

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      John Wiley & Sons, Hoboken, 2013. 392 pp., hardcover, € 119.00.—ISBN 978-1118183656

  10. Highlight

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    14. Communications
    1. Prebiotic Chemistry

      Citric Acid and the RNA World (pages 5245–5247)

      Prof. Ulrich F. Müller and Prof. Yitzhak Tor

      Version of Record online: 14 MAY 2014 | DOI: 10.1002/anie.201400847

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      RNA world: The chelation of magnesium ions by citric acid prevents the magnesium-induced aggregation of lipid vesicles and RNA degradation while promoting nonenzymatic RNA oligomerization. These findings suggest a unique role for this simple organic acid in supporting key processes in RNA world organisms.

  11. Minireview

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    14. Communications
    1. Natural Product Synthesis

      Biosynthesis and Chemical Synthesis of Presilphiperfolanol Natural Products (pages 5248–5260)

      Allen Y. Hong and Prof. Brian M. Stoltz

      Version of Record online: 25 APR 2014 | DOI: 10.1002/anie.201309494

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      All in the family: The presilphiperfolane skeleton is an important intermediate in the diverging biosynthetic pathways leading to numerous sesquiterpene natural products. Research in natural products, biosynthetic, and computational chemistry has provided much insight into the major skeletal rearrangement mechanisms. Advances in synthetic organic chemistry have enabled access to several members of the presilphiperfolanol family by total synthesis and contributed to current understanding.

  12. Review

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    14. Communications
    1. Materials Science

      Carbon Fibers: Precursor Systems, Processing, Structure, and Properties (pages 5262–5298)

      Dr.  Erik Frank, Dipl.-Chem. Lisa M. Steudle, Dr. Denis Ingildeev, Dipl.-Chem. Johanna M. Spörl and Prof. Michael R. Buchmeiser

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201306129

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      Strand and deliver: Different precursor systems for the synthesis of carbon fibers, their processing, and the properties of the resulting carbon fibers with respect to the precursor used as well as the latest developments in alternative precursor systems are presented.

  13. Communications

    1. Top of page
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    14. Communications
    1. Heterolytic H2 Cleavage | Very Important Paper

      Heterolytic Cleavage of Hydrogen by an Iron Hydrogenase Model: An Fe-H⋅⋅⋅H-N Dihydrogen Bond Characterized by Neutron Diffraction (pages 5300–5304)

      Dr. Tianbiao Liu, Dr. Xiaoping Wang, Dr. Christina Hoffmann, Dr. Daniel L. DuBois and Dr. R. Morris Bullock

      Version of Record online: 22 APR 2014 | DOI: 10.1002/anie.201402090

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      Caught in the act: The addition of H2 to a synthetic iron complex containing a pendant amine (a model complex for [FeFe] hydrogenase) leads to facile heterolytic cleavage of H2. Neutron diffraction indicates a very short H⋅⋅⋅H bond distance of 1.489(10) Å in the Fe-H⋅⋅⋅H-N complex, thus providing a glimpse of how the H[BOND]H bond is oxidized in hydrogenase enzymes.

    2. Hydroazidation

      Silver(I)-Catalyzed Hydroazidation of Ethynyl Carbinols: Synthesis of 2-Azidoallyl Alcohols (pages 5305–5309)

      Zhenhua Liu, Jianquan Liu, Lin Zhang, Dr. Peiqiu Liao, Prof. Jinna Song and Prof. Xihe Bi

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201310264

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      Azides and aziridines: The hydroazidation of unactivated alkynes by means of silver catalysis is described. A variety of ethynyl carbinols are capable of reacting with trimethylsilyl azide to produce 2-azidoallyl alcohols in good to excellent yields. The synthetic utility of 2-azidoallyl alcohols was demonstrated by further conversion into NH aziridines.

    3. Magnetic Anisotropy

      Large Zero-Field Splittings of the Ground Spin State Arising from Antisymmetric Exchange Effects in Heterometallic Triangles (pages 5310–5313)

      Samantha A. Magee, Dr. Stephen Sproules, Dr. Anne-Laure Barra, Dr. Grigore A. Timco, Nicholas F. Chilton, Prof. David Collison, Prof. Richard E. P. Winpenny and Prof. Eric J. L. McInnes

      Version of Record online: 15 APR 2014 | DOI: 10.1002/anie.201400655

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      Zeroing in: By using [RuIII2MnII(O)(tBuCO2)6(py)3] as an example, antisymmetric exchange effects have been shown to lead to very large spin ground-state zero-field splittings in polymetallic complexes. The zero-field splitting of the S=5/2 ground state of the heterometallic oxo-centered triangle has been measured as D=3 cm−1, an order of magnitude larger than found for the {Fe2Mn} analogue.

    4. NHC Catalysis

      Cascade Olefin Isomerization/Intramolecular Diels–Alder Reaction Catalyzed by N-Heterocyclic Carbenes (pages 5314–5317)

      Marcin Kowalczyk and Dr. David W. Lupton

      Version of Record online: 6 APR 2014 | DOI: 10.1002/anie.201402067

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      NHC-catalyzed cascade: The addition of an N-heterocyclic carbene (NHC) to the carbonyl group of an α,β,γ,δ-unsaturated enol ester affords a hemiacetal azolium intermediate that enables a cascade olefin isomerization/Diels–Alder reaction. Preliminary studies into the utility of the products using reductive and oxidative cleavage gave substrates for potential use in the synthesis of complex targets.

    5. Bioinorganic Chemistry

      A Bio-Inspired Switch Based on Cobalt(II) Disulfide/Cobalt(III) Thiolate Interconversion (pages 5318–5321)

      Dr. Marcello Gennari, Bertrand Gerey, Dr. Nikita Hall, Dr. Jacques Pécaut, Dr. Marie-Noëlle Collomb, Mathieu Rouzières, Dr. Rodolphe Clérac, Dr. Maylis Orio and Dr. Carole Duboc

      Version of Record online: 9 APR 2014 | DOI: 10.1002/anie.201402125

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      A switchable CoII2 disulfide/CoIII thiolate system (see scheme; filled circles show the color change) is stable under aerobic conditions. It offers the chance to understand the disulfide/thiolate interconversion supported by transition-metal ions, which is proposed to be involved in various fundamental biological processes.

    6. Anti-Aging Membranes

      Ending Aging in Super Glassy Polymer Membranes (pages 5322–5326)

      Dr. Cher Hon Lau, Dr. Phuc Tien Nguyen, Dr. Matthew R. Hill, Dr. Aaron W. Thornton, Dr. Kristina Konstas, Dr. Cara M. Doherty, Dr. Roger J. Mulder, Dr. Laure Bourgeois, Dr. Amelia C. Y. Liu, Dr. David J. Sprouster, Prof. James P. Sullivan, Dr. Timothy J. Bastow, Dr. Anita J. Hill, Prof. Douglas L. Gin and Prof. Richard D. Noble

      Version of Record online: 16 APR 2014 | DOI: 10.1002/anie.201402234

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      Forever young: Like stringed beads, polymer chains of a permeable membrane are intercalated within the pores of PAF-1 particles thus inhibiting polymer chain relaxation and stopping aging. PAF-1 incorporation also drastically enhanced gas permeabilities (see picture).

    7. Asymmetric Catalysis

      Direct Catalytic Asymmetric Vinylogous Conjugate Addition of Unsaturated Butyrolactones to α,β-Unsaturated Thioamides (pages 5327–5331)

      Dr. Liang Yin, Dr. Hisashi Takada, Shaoquan Lin, Dr. Naoya Kumagai and Prof. Dr. Masakatsu Shibasaki

      Version of Record online: 16 APR 2014 | DOI: 10.1002/anie.201402332

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      Soft spot: Soft Lewis acid/Brønsted base cooperative catalysts have enabled the title reaction of α,β- and β,γ-unsaturated butyrolactones with perfect atom economy. When using α-angelica lactone and its derivatives as pronucleophiles, a 0.5 mol % catalyst loading was sufficient to complete the reaction to construct consecutive tri- and tetrasubstituted stereogenic centers in a highly diastereo- and enantioselective fashion.

    8. Natural Products

      An Enantiospecific Synthesis of Jiadifenolide (pages 5332–5335)

      David A. Siler, Jeffrey D. Mighion and Prof. Erik J. Sorensen

      Version of Record online: 23 APR 2014 | DOI: 10.1002/anie.201402335

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      Establishing the framework: A Robinson annulation, van Leusen homologation, and a desymmetrizing C[BOND]H oxidation enabled an enantiospecific synthesis of the neurotrophic natural product jiadifenolide. From a pulegone-derived building block, a key propellane intermediate was constructed through the use of simple reagents in a highly diastereoselective fashion. A short series of oxidations of this tricylic framework allowed progression to the natural product.

    9. Mixed-Oxide Catalysts | Hot Paper

      Stabilization of Catalytically Active Cu+ Surface Sites on Titanium–Copper Mixed-Oxide Films (pages 5336–5340)

      Dr. Ashleigh E. Baber, Dr. Xiaofang Yang, Dr. Hyun You Kim, Dr. Kumudu Mudiyanselage, Markus Soldemo, Dr. Jonas Weissenrieder, Dr. Sanjaya D. Senanayake, Dr. Abdullah Al-Mahboob, Dr. Jerzy T. Sadowski, Dr. Jaime Evans, Dr. José A. Rodriguez, Dr. Ping Liu, Dr. Friedrich M. Hoffmann, Dr. Jingguang G. Chen and Dr. Darío J. Stacchiola

      Version of Record online: 9 APR 2014 | DOI: 10.1002/anie.201402435

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      Positively active: Copper oxide based structures were the first that could catalyze the oxidation of CO at room temperature. Their deactivation, however, is facile, because the required Cu+ state cannot be preserved under the reaction conditions. The addition of the right amount of titanium leads to mixed CuTiOx films that are thermally and chemically stable and more active CO oxidation catalysts than pure copper oxide materials.

    10. Sodium-Ion Battery

      Polymeric Schiff Bases as Low-Voltage Redox Centers for Sodium-Ion Batteries (pages 5341–5345)

      Dr. Elizabeth Castillo-Martínez, Dr. Javier Carretero-González and Prof. Michel Armand

      Version of Record online: 22 APR 2014 | DOI: 10.1002/anie.201402402

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      Energy storage: Simple polymeric Schiff bases insert sodium ions at low potential with high capacities. More than one sodium ion can be reversibly stored per C[DOUBLE BOND]N bond in polymeric Schiff bases (see picture) with the active unit [BOND]N[DOUBLE BOND]CH[BOND]Ar[BOND]HC[DOUBLE BOND]N[BOND] that contains ten π electrons.

    11. Extractant Aggregation

      Elucidation of the Structure of Organic Solutions in Solvent Extraction by Combining Molecular Dynamics and X-ray Scattering (pages 5346–5350)

      Dr. Geoffroy Ferru, Donatien Gomes Rodrigues, Dr. Laurence Berthon, Dr. Olivier Diat, Dr. Pierre Bauduin and Dr. Philippe Guilbaud

      Version of Record online: 11 APR 2014 | DOI: 10.1002/anie.201402677

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      A terrific team: The ill-defined self-aggregation of metal-ion extractants in oils was determined by using a combination of molecular-dynamics simulation and small-/wide-angle X-ray scattering (SWAXS) techniques (see picture). In this way, it was possible to quantitatively describe the molecular and supramolecular organization of the extractant in the organic phase at a wide range of concentrations.

    12. Supramolecular Polymers

      Supramolecular Polymerization Promoted and Controlled through Self-Sorting (pages 5351–5355)

      Zehuan Huang, Liulin Yang, Yiliu Liu, Prof. Zhiqiang Wang, Dr. Oren A. Scherman and Prof. Xi Zhang

      Version of Record online: 7 APR 2014 | DOI: 10.1002/anie.201402817

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      Got it under control: A method in which supramolecular polymerization is controlled through self-sorting is reported. The p-phenylene (green circles) and naphthalene (blue ovals) moieties of the bifunctional monomer are selectively recognized by cucurbit[7]uril (green barrels) and cucurbit[8]uril (blue barrels), respectively. The processes of polymerization and degradation can be controlled by tuning the cucurbit[7]uril content.

    13. Photoredox Catalysis

      Visible-Light-Induced Photoredox Catalysis with a Tetracerium-Containing Silicotungstate (pages 5356–5360)

      Dr. Kosuke Suzuki, Fei Tang, Dr. Yuji Kikukawa, Dr. Kazuya Yamaguchi and Prof. Dr. Noritaka Mizuno

      Version of Record online: 16 APR 2014 | DOI: 10.1002/anie.201403215

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      Cerium, silicon, tungsten: Intramolecular CeIII-to-POM(WVI) charge transfer is observed when the tetranuclear cerium(III)-containing silicotungstate CePOM is irradiated with visible light (λ>400 nm; POM=polyoxometalate). This enabled the photocatalytic oxidative dehydrogenation of primary and secondary amines as well as the α-cyanation of tertiary amines in the presence of O2 (1 atm) as the sole oxidant.

    14. Fluorescence Sensing

      Pattern-Based Detection of Toxic Metals in Surface Water with DNA Polyfluorophores (pages 5361–5365)

      Lik Hang Yuen, Dr. Raphael M. Franzini, Dr. Shenliang Wang, Dr. Pete Crisalli, Dr. Vijay Singh, Dr. Wei Jiang and Prof. Dr. Eric T. Kool

      Version of Record online: 22 APR 2014 | DOI: 10.1002/anie.201403235

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      Detecting metal contamination in surface/ground water is crucial for protecting human health. The design and synthesis of metal-binding fluorescent nucleosides and development of a sensor array with DNA-polyfluorophores on beads is described, as well as their ability to detect and differentiate environmental contaminants in water.

    15. Mesoporous Nanospheres

      Dual-Pore Mesoporous Carbon@Silica Composite Core–Shell Nanospheres for Multidrug Delivery (pages 5366–5370)

      Yin Fang, Prof. Gengfeng Zheng, Jianping Yang, Haosha Tang, Yafeng Zhang, Biao Kong, Yingying Lv, Prof. Congjian Xu, Prof. Abdullah M. Asiri, Prof. Jian Zi, Prof. Fan Zhang and Prof. Dongyuan Zhao

      Version of Record online: 24 APR 2014 | DOI: 10.1002/anie.201402002

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      Novel nanocarriers benefit from their hierarchical mesostructure and dual-pore mesochannels, and the amphiphilicity of the hydrophobic carbon cores and hydrophilic silica shells. These composite nanospheres can be loaded with cisplatin and paclitaxel in multidrug combination therapy for the treatment of human ovarian cancer.

    16. Electron Transfer

      Electron Transfer and Multi-Electron Accumulation in ExBox4+ (pages 5371–5375)

      Scott M. Dyar, Jonathan C. Barnes, Dr. Michal Juríček, Prof. J. Fraser Stoddart, Prof. Dick T. Co, Prof. Ryan M. Young and Prof. Michael R. Wasielewski

      Version of Record online: 14 MAY 2014 | DOI: 10.1002/anie.201402444

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      From outside the box: A viologen-based cyclophane ExBox4+ is photoexcited revealing a new through-bond pathway for electron transfer to ExBox4+. The solid-state structure with both redox states ExBox4+ and ExBox2+ present, confirms that transferred electrons cause ExBox2+ to become flattened and form semiquinoidal structures capable of stabilizing unpaired electrons.

    17. Coil–Helix Transition

      You have full text access to this OnlineOpen article
      Unravelling Secondary Structure Changes on Individual Anionic Polysaccharide Chains by Atomic Force Microscopy (pages 5376–5379)

      Larissa Schefer, Dr. Jozef Adamcik and Prof. Dr. Raffaele Mezzenga

      Version of Record online: 16 APR 2014 | DOI: 10.1002/anie.201402855

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      The coil–helix transition within single chains of anionic carrageenan polysaccharides is resolved in situ by atomic force microscopy, as a result of the presence of monovalent ions close to physiological conditions (see picture). Polymer statistical analysis demonstrates a modulation of the rigidity and topological features of individual polyelectrolyte chains upon this conformational change.

    18. Nanocomposites

      In Situ Synthesis of Robust Conductive Cellulose/Polypyrrole Composite Aerogels and Their Potential Application in Nerve Regeneration (pages 5380–5384)

      Zhuqun Shi, Huichang Gao, Jiao Feng, Beibei Ding, Prof. Xiaodong Cao, Prof. Shigenori Kuga, Prof. Yingjun Wang, Prof. Lina Zhang and Prof. Jie Cai

      Version of Record online: 7 APR 2014 | DOI: 10.1002/anie.201402751

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      Composite gels prepared from nanoporous cellulose gel and in situ formed polypyrrole nanoparticles have low density, large surface area, high mechanical strength, sufficient electrical conductivity, no cytotoxicity, and neural differentiation ability. This robust conductive gel/aerogel will be useful for the development of materials for nerve regeneration, carbon capture, catalyst supports, and many other applications.

    19. Asymmetric Catalysis

      Asymmetric Hydrogenation of Maleic Acid Diesters and Anhydrides (pages 5385–5388)

      Dr. Maurizio Bernasconi, Marc-André Müller and Prof. Dr. Andreas Pfaltz

      Version of Record online: 7 APR 2014 | DOI: 10.1002/anie.201402034

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      An attractive enantioselective route to 2-alkyl- and 2-aryl-substituted succinic acid derivatives is opened up by the asymmetric hydrogenation of maleic and fumaric acid derivatives, using the new catalyst [Ir(cod)L]BArF, derived from a 2,6-difluorophenyl-substituted pyridine-phosphinite ligand. The products are valuable chiral building blocks having a structural motif found in many bioactive compounds. cod=1,5-cyclooctadiene.

    20. Peptide Synthesis

      Inverse Peptide Synthesis via Activated α-Aminoesters (pages 5389–5393)

      Jean-Simon Suppo, Prof. Dr. Gilles Subra, Matthieu Bergès, Dr. Renata Marcia de Figueiredo and Prof. Dr. Jean-Marc Campagne

      Version of Record online: 23 APR 2014 | DOI: 10.1002/anie.201402147

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      How to advance by going into reverse: In a mild and practical procedure for peptide-bond formation, free α-aminoesters were activated by treatment with N,N′-carbonyldiimidazole, instead of activating the carboxylic acid functionality (see scheme). The method provided a straightforward route to dipeptides, and its applicability to iterative peptide synthesis was illustrated by the synthesis of a tetrapeptide in the challenging reverse N[RIGHTWARDS ARROW]C direction.

    21. Carbon Nanotubes

      Mechanically Interlocked Single-Wall Carbon Nanotubes (pages 5394–5400)

      Alberto de Juan, Dr. Yann Pouillon, Dr. Luisa Ruiz-González, Dr. Almudena Torres-Pardo, Dr. Santiago Casado, Prof. Dr. Nazario Martín, Prof. Dr. Ángel Rubio and Dr. Emilio M. Pérez

      Version of Record online: 11 APR 2014 | DOI: 10.1002/anie.201402258

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      Nanotubes in MINT condition! In a clipping reaction, macrocycles were formed by ring-closing metathesis around single-wall nanotubes (SWNTs) as “threads” to produce rotaxane-type species: mechanically interlocked derivatives of carbon nanotubes (MINTs; see picture). Extensive characterization, including high-resolution STEM and control experiments, proved the interlocked nature of the products.

    22. Natural Product Synthesis

      A Rapid Synthesis of 4-Oxazolidinones: Total Synthesis of Synoxazolidinones A and B (pages 5401–5404)

      Nataliia V. Shymanska, Il Hwan An and Prof. Joshua G. Pierce

      Version of Record online: 7 APR 2014 | DOI: 10.1002/anie.201402310

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      Synthetic synoxazolidinones: A five-step total synthesis of the marine natural product synoxazolidinone A was achieved through a diastereoselective imine acylation/cyclization cascade. Synoxazolidinone B and a series of analogues were also prepared to explore the potential of these 4-oxazolidinones as antimicrobial agents. The results revealed simplified dichloro derivatives that are equally potent against several bacterial strains.

    23. Weak Interactions

      The Experimental Observation of the Intramolecular NO2/CO Interaction in Solution (pages 5405–5409)

      Dr. Michel Chiarucci, Dr. Alessia Ciogli, Dr. Michele Mancinelli, Silvia Ranieri and Prof. Dr. Andrea Mazzanti

      Version of Record online: 9 APR 2014 | DOI: 10.1002/anie.201402366

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      Might without muscle: The weak electrostatic interaction between nitro and carbonyl moieties has been observed by means of variable-temperature NMR spectroscopy. Its energetic contribution was evaluated to be about 3 kcal mol−1 by DFT calculations, and confirmed by the measurement of internal energy barriers to the rotation of suitable nitroaryl rings (see picture).

    24. C[BOND]H Activation

      Iridium-Catalyzed Enantioselective C[BOND]H Alkylation of Ferrocenes with Alkenes Using Chiral Diene Ligands (pages 5410–5413)

      Prof. Dr. Takanori Shibata and Tsubasa Shizuno

      Version of Record online: 11 APR 2014 | DOI: 10.1002/anie.201402518

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      Director's cut: The first catalytic and enantioselective C[BOND]H alkylation of ferrocene derivatives with various alkenes was achieved. A cationic iridium complex, having a chiral diene ligand, and an isoquinolyl moiety as a directing group are essential for regioselective and enantioselective C[BOND]H bond activation. coe=cyclooctene, NaBARF=sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate.

    25. Cyclization

      Boron Perturbed Click Reactions Prompt Aromatic C[BOND]H Activations (pages 5414–5417)

      Dr. Daniel Winkelhaus and Prof. Dr. Douglas W. Stephan

      Version of Record online: 11 APR 2014 | DOI: 10.1002/anie.201402567

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      Click on B: The reaction of bis(pentafluorophenyl)boron alkynes and azides leads to unusual N3BC heterocycles (see scheme) resulting from aromatic C[BOND]H activation of benzene and toluene. While subsequent treatment of the heterocycle with PMe3 gave the P[BOND]B adduct, reaction with PtBu3 effected deprotonation to generate the corresponding phosphonium salt.

    26. Homogeneous Catalysis

      Synthesis of Cyclic Amine Boranes through Triazole-Gold(I)-Catalyzed Alkyne Hydroboration (pages 5418–5422)

      Qiaoyi Wang, Stephen E. Motika, Dr. Novruz G. Akhmedov, Prof. Jeffrey L. Petersen and Prof. Xiaodong Shi

      Version of Record online: 9 APR 2014 | DOI: 10.1002/anie.201402614

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      Stable and active: The first catalytic alkyne hydroboration of propargyl amine boranecarbonitrile is accomplished. While the typical [L-Au]+ species decomposed within minutes upon addition of amine boranecarbonitriles, the triazole-modified gold catalysts (TA-Au) remained active and allowed formation of 1,2-BN-cyclopentenes in excellent yields.

    27. Polyketide Biosynthesis

      Biosynthesis of the Structurally Unique Polycyclopropanated Polyketide–Nucleoside Hybrid Jawsamycin (FR-900848) (pages 5423–5426)

      Dr. Tomoshige Hiratsuka, Hideaki Suzuki, Ryo Kariya, Takashi Seo, Dr. Atsushi Minami and Prof. Dr. Hideaki Oikawa

      Version of Record online: 23 APR 2014 | DOI: 10.1002/anie.201402623

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      Jaws of life: The biosynthetic gene cluster of antifungal agent jawsamycin (FR-900848) has been identified by heterologous expression. A series of gene inactivations and in vitro and in vivo analysis of the key enzymes established their functions. A novel iterative polyketide synthase is proposed to collaborate with a trans-acting ketoreductase and a radical SAM cyclopropanase in constructing the unique polycyclopropanated backbone.

    28. Hydrogen Evolution | Hot Paper

      Highly Active Electrocatalysis of the Hydrogen Evolution Reaction by Cobalt Phosphide Nanoparticles (pages 5427–5430)

      Eric J. Popczun, Carlos G. Read, Christopher W. Roske, Prof. Nathan S. Lewis and Prof. Raymond E. Schaak

      Version of Record online: 11 APR 2014 | DOI: 10.1002/anie.201402646

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      One step closer to Pt: Nanoparticles of cobalt phosphide (CoP) catalyze the hydrogen evolution reaction with high activity and stability under strongly acidic conditions. Its electrocatalytic performance places CoP amongst the best Earth-abundant alternatives to platinum.

    29. Polyazides

      Coordination Adducts of Niobium(V) and Tantalum(V) Azide M(N3)5 (M=Nb, Ta) with Nitrogen Donor Ligands and their Self-Ionization (pages 5431–5434)

      Prof. Dr. Ralf Haiges, Piyush Deokar and Prof. Dr. Karl O. Christe

      Version of Record online: 22 APR 2014 | DOI: 10.1002/anie.201402775

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      Several donor–acceptor adducts of niobium and tantalum pentaazide with N-donor ligands have been prepared from the pentafluorides by fluoride–azide exchange with Me3SiN3 in the presence of the corresponding donor ligand. With 2,2′-bipyridine and 1,10-phenanthroline, self-ionization products were formed, whereas 3,3′- and 4,4′-bipyridine gave neutral pentaazide adducts (M(N3)5)2⋅L (see picture).

    30. Asymmetric Catalysis

      Highly Diastereo- and Enantioselective Silver-Catalyzed Double [3+2] Cyclization of α-Imino Esters with Isocyanoacetate (pages 5435–5439)

      Dr. Pan-Lin Shao, Jia-Yu Liao, Yee Ann Ho and Prof. Yu Zhao

      Version of Record online: 22 APR 2014 | DOI: 10.1002/anie.201402788

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      Double up: An unprecedented silver-catalyzed title reaction has been developed and provides access to directly linked oxazole-imidazolines. A highly diastereo- and enantioselective variant was also realized using the catalyst Ag/L*. The products can be easily transformed into highly functionalized chiral α,β-diamino esters or imidazolinium salts which are useful motifs in asymmetric synthesis and catalysis.

    31. Hydrocarbons

      Tetravinylethylene (pages 5440–5443)

      Erik J. Lindeboom, Dr. Anthony C. Willis, Prof. Michael N. Paddon-Row and Prof. Michael S. Sherburn

      Version of Record online: 23 APR 2014 | DOI: 10.1002/anie.201402840

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      Targets very efficiently: The forgotten hydrocarbon, tetravinylethylene (TVE, scheme) is a bench-stable compound that can be synthesized in one step from commercially available starting materials. TVE is a vehicle for rapid complex molecule synthesis through one-pot sequences involving the stereoselective assembly of up to seven C[BOND]C bonds.

    32. Homogeneous Catalysis

      Gold-Catalyzed 1,2-Oxoarylations of Nitriles with Pyridine-Derived Oxides (pages 5444–5448)

      Somnath Narayan Karad and Prof. Dr. Rai-Shung Liu

      Version of Record online: 22 APR 2014 | DOI: 10.1002/anie.201403015

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      Spill the (car)benes: Reported herein is the first successful gold-catalyzed oxoarylation of nitriles with pyridine-derived N-oxides using gold carbenes as initiators (see scheme; DCE=1,2-dichloroethane, IPr=1,3-bis(diisopropylphenyl)imidazol-2-ylidene). These oxoarylations were also achieved satisfactorily in intermolecular three-component oxidations using a variety of alkenyldiazo esters, nitriles, and pyridine-based N-oxides.

    33. Organocatalysis

      Remote Enantioselective Friedel–Crafts Alkylations of Furans through HOMO Activation (pages 5449–5452)

      Jun-Long Li, Cai-Zhen Yue, Peng-Qiao Chen, You-Cai Xiao and Prof. Dr. Ying-Chun Chen

      Version of Record online: 22 APR 2014 | DOI: 10.1002/anie.201403082

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      Alternative strategy: An asymmetric and regioselective Friedel–Crafts alkylation reaction of 2-furfuryl ketones and alkylidenemalononitriles was developed and involves the in situ generation of a formal HOMO-raised trienamine species. A diversity of alkylation products were produced in moderate to excellent enantioselectivity under the catalysis of a chiral bifunctional primary amine-thiourea (1).

    34. Boron Radicals

      Evidence for Extensive Single-Electron-Transfer Chemistry in Boryl Anions: Isolation and Reactivity of a Neutral Borole Radical (pages 5453–5457)

      Dr. Rüdiger Bertermann, Prof. Dr. Holger Braunschweig, Dr. Rian D. Dewhurst, Dipl.-Chem. Christian Hörl, Dipl.-Chem. Thomas Kramer and Dr. Ivo Krummenacher

      Version of Record online: 9 APR 2014 | DOI: 10.1002/anie.201402556

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      ReSETting perspectives: A borolyl anion displays single-electron-transfer (SET) processes in its reaction with triorganotetrel halides. This was confirmed by the isolation of the first neutral borolyl radical. This radical reactivity was exploited in the synthesis of compounds with rare B[BOND]Sn and B[BOND]Pb bonds, the latter of which is the first structurally characterized species with a “noncluster” B[BOND]Pb bond.

    35. Synthetic Methods | Hot Paper

      Organocatalytic Atroposelective Aldol Condensation: Synthesis of Axially Chiral Biaryls by Arene Formation (pages 5458–5461)

      Achim Link and Dr. Christof Sparr

      Version of Record online: 23 APR 2014 | DOI: 10.1002/anie.201402441

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      Head-turning! An organocatalytic atroposelective aldol condensation to tri-ortho-substituted biaryls is described. Key to the process is an efficient transfer of the stereochemical information of a secondary amine catalyst into the axis of chirality of binaphthyl products. The reaction proceeds analogous to the aromatic polyketide biosynthesis and is distinct in its initiation by virtue of dienamine formation. This method allows for the synthesis of axially chiral biaryls with remarkable atroposelectivity of up to e.r. 99:1.

    36. Amide Activation | Very Important Paper

      Chemoselective Intermolecular α-Arylation of Amides (pages 5462–5466)

      Dr. Bo Peng, Dr. Danny Geerdink, Dr. Christophe Farès and Prof. Dr. Nuno Maulide

      Version of Record online: 16 APR 2014 | DOI: 10.1002/anie.201402229

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      Arylating me softly: A new approach for the fully chemoselective α-arylation of amides has been developed. When electrophilic amide activation is employed, aryl groups can be regioselectively introduced in the position α to the amide, and that even in the presence of esters or alkyl ketones. Mechanistic studies emphasize a remarkably subtle base effect in this transformation.

    37. CO Methanation

      The Origin of the Selectivity and Activity of Ruthenium-Cluster Catalysts for Fuel-Cell Feed-Gas Purification: A Gas-Phase Approach (pages 5467–5471)

      Dr. Sandra M. Lang, Prof. Dr. Thorsten M. Bernhardt, Marjan Krstić and Prof. Dr. Vlasta Bonačić-Koutecký

      Version of Record online: 6 MAY 2014 | DOI: 10.1002/anie.201310134

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      Be selective! Efficient CO methanation catalysts for fuel-cell feed-gas purification have to selectively convert CO while leaving CO2 untouched. Employing free clusters as model systems, mechanistic insights are obtained that provide the basis for understanding and improving the performance of supported ruthenium catalysts in this reaction (see picture: Ru green, C gray, H white, O red).

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