Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 28

July 7, 2014

Volume 53, Issue 28

Pages 7091–7367

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Review
    12. Communications
    1. You have free access to this content
      Cover Picture: Chinese Puzzle Molecule: A 15 Hydride, 28 Copper Atom Nanoball (Angew. Chem. Int. Ed. 28/2014) (page 7091)

      Dr. Alison J. Edwards, Dr. Rajendra S. Dhayal, Dr. Ping-Kuei Liao, Jian-Hong Liao, Dr. Ming-Hsi Chiang, Dr. Ross O. Piltz, Dr. Samia Kahlal, Prof. Jean-Yves Saillard and Prof. C. W. Liu

      Version of Record online: 18 MAY 2014 | DOI: 10.1002/anie.201405105

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      Dithiolato-protected copper hydride nanoclusters that evolve hydrogen under sunlight irradiation were prepared. As C. W. Liu and co-workers describe in their Communication on page 7214 ff., these nanoclusters were structurally characterized by various spectroscopic methods, including single-crystal neutron diffraction. The onion-like structure displays a geometric entity that is reminiscent of a Chinese puzzle ball.

    2. You have free access to this content
      Inside Cover: [3+2] Cycloaddition of Propargylic Alcohols and α-Oxo Ketene Dithioacetals: Synthesis of Functionalized Cyclopentadienes and Further Application in a Diels–Alder Reaction (Angew. Chem. Int. Ed. 28/2014) (page 7092)

      Zhongxue Fang, Jianquan Liu, Prof. Qun Liu and Prof. Xihe Bi

      Version of Record online: 28 MAY 2014 | DOI: 10.1002/anie.201405097

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      Functionalized cyclopentadienes can be synthesized by a novel [3+2] cycloaddition of propargylic alcohols and ketene dithioacetals, as X. Bi and co-workers report in their Communication on page 7209 ff. Fully substituted 2,5-dialkylthio cyclopentadienes were obtained in good to excellent yields. Furthermore, these cyclopentadienes reacted with maleimides in an unusual dethiolating Diels–Alder reaction, which afforded novel fluorescent polycyclic compounds.

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      Inside Back Cover: Be2C Monolayer with Quasi-Planar Hexacoordinate Carbons: A Global Minimum Structure (Angew. Chem. Int. Ed. 28/2014) (page 7369)

      Prof. Dr. Yafei Li, Yunlong Liao and Prof. Dr. Zhongfang Chen

      Version of Record online: 26 MAY 2014 | DOI: 10.1002/anie.201405103

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      By density functional calculations a new inorganic two-dimensional material, namely the Be2C monolayer, was designed. In their Communication on page 7248 ff., Y. Li, Y. Liao, and Z. Chen show that in the Be2C monolayer each C atom binds to six Be atoms to form a quasi-planar hexacoordinate carbon moiety. Be2C is predicted to be stable and to have promising applications in electronics and optoelectronics.

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      Back Cover: Sugar-based Molecular Computing by Material Implication (Angew. Chem. Int. Ed. 28/2014) (page 7370)

      Martin Elstner, Jörg Axthelm and Prof.Dr. Alexander Schiller

      Version of Record online: 16 JUN 2014 | DOI: 10.1002/anie.201405137

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      Molecular logic and computing are based on the principles derived by Prof. Frege (University of Jena, 1848–1925). A. Schiller and co-workers present in their Communication on page 7339 ff. a method to integrate an (in principle) unlimited number of molecular logic gates to construct complex circuits on microtiter plates. Using a fluorescent boronic acid fructose probe and the FALSE operation, an external wiring algorithm translates the fluorescent output from one gate into a chemical input for the next gate by pipetting steps.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Review
    12. Communications
    1. You have free access to this content
      Frontispiece: Combining Photoredox-Catalyzed Trifluoromethylation and Oxidation with DMSO: Facile Synthesis of α-Trifluoromethylated Ketones from Aromatic Alkenes (page 7092)

      Ren Tomita, Dr. Yusuke Yasu, Dr. Takashi Koike and Prof. Dr. Munetaka Akita

      Version of Record online: 2 JUL 2014 | DOI: 10.1002/anie.201482871

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      In their Communication on page 7144 ff., T. Koike, M. Akita et al. describe the synthesis of valuable α-CF3-substituted ketones from aromatic alkenes by combining photoredox-catalyzed trifluoromethylation and oxidation with DMSO.

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Review
    12. Communications
  4. Corrigenda

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Review
    12. Communications
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    2. You have free access to this content
      Corrigendum: Multifunctional Nanoprobes for Nanoscale Chemical Imaging and Localized Chemical Delivery at Surfaces and Interfaces (page 7109)

      Dr. Yasufumi Takahashi, Dr. Andrew I. Shevchuk, Dr. Pavel Novak, Prof. Yanjun Zhang, Neil Ebejer, Prof. Julie V. Macpherson, Prof. Patrick R. Unwin, Dr. Andrew J. Pollard, Dr. Debdulal Roy, Dr. Charles A. Clifford, Dr. Hitoshi Shiku, Prof. Tomokazu Matsue, Prof. David Klenerman and Prof. Yuri E. Korchev

      Version of Record online: 2 JUL 2014 | DOI: 10.1002/anie.201404979

      This article corrects:
  5. News

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Review
    12. Communications
  6. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Review
    12. Communications
    1. Nazario Martín (pages 7116–7117)

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201402748

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      “My biggest motivation is the best is yet to come! If I were not a scientist, I would be a writer or actor—or maybe a bishop …” This and more about Nazario Martín can be found on page 7116.

  7. News

    1. Top of page
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    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Review
    12. Communications
  8. Book Review

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
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    9. Book Review
    10. Highlight
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    12. Communications
    1. Modern Nucleophilic Aromatic Substitution. By Francois Terrier. (page 7119)

      Herbert Mayr

      Version of Record online: 20 MAY 2014 | DOI: 10.1002/anie.201404183

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      Wiley-VCH, Weinheim, 2013. 488 pp., hardcover, € 150.00.—ISBN 978-3527318612

  9. Highlight

    1. Top of page
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    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
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    9. Book Review
    10. Highlight
    11. Review
    12. Communications
    1. Electroorganic Synthesis

      Renaissance of Electrosynthetic Methods for the Construction of Complex Molecules (pages 7122–7123)

      Prof. Dr. Siegfried R. Waldvogel and Dr. Birgit Janza

      Version of Record online: 18 JUN 2014 | DOI: 10.1002/anie.201405082

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      Current affairs: Efficient N,N dimerization by using an electric current is a recent powerful example of preparative electrosynthesis where conventional reagents fail. The general and practical nature of this method as well as other applications will breathe new life into the electroorganic synthesis of complex molecules.

  10. Review

    1. Top of page
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    5. Corrigenda
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    12. Communications
    1. Chemistry of Smell

      Nature’s Chemical Signatures in Human Olfaction: A Foodborne Perspective for Future Biotechnology (pages 7124–7143)

      Andreas Dunkel, Dr. Martin Steinhaus, Matthias Kotthoff, Bettina Nowak, Priv.-Doz. Dr. Dietmar Krautwurst, Prof. Dr. Peter Schieberle and Prof. Dr. Thomas Hofmann

      Version of Record online: 18 JUN 2014 | DOI: 10.1002/anie.201309508

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      The sheer unlimited variation in biologically relevant chemosensory entities are defined by a “combinatorial odor code”, which comprises a central group of up to 40 out of the circa 230 high impact odorants that have been identified. This suggests the foodborne stimulus space to have co-evolved with, and roughly match our circa 400 olfactory receptors (see picture: odor-specific receptor activity pattern; OR=olfactory receptor).

  11. Communications

    1. Top of page
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    3. Frontispiece
    4. Graphical Abstract
    5. Corrigenda
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlight
    11. Review
    12. Communications
    1. Keto-Trifluoromethylation

      Combining Photoredox-Catalyzed Trifluoromethylation and Oxidation with DMSO: Facile Synthesis of α-Trifluoromethylated Ketones from Aromatic Alkenes (pages 7144–7148)

      Ren Tomita, Dr. Yusuke Yasu, Dr. Takashi Koike and Prof. Dr. Munetaka Akita

      Version of Record online: 26 MAY 2014 | DOI: 10.1002/anie.201403590

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      Valuable α-CF3-substituted ketones can be synthesized from aromatic alkenes by combining photoredox-catalyzed trifluoromethylation and oxidation with DMSO. The iridium photocatalyst fac-[Ir(ppy)3] (ppy=2-phenylpyridine) plays key roles in this keto-trifluoromethylation. SET=single electron transfer.

    2. Enzyme Substrates

      Substrate Profiling of Glutathione S-transferase with Engineered Enzymes and Matched Glutathione Analogues (pages 7149–7153)

      Dr. Shan Feng, Lei Zhang, Gulishana Adilijiang, Jieyuan Liu, Prof. Minkui Luo and Prof. Haiteng Deng

      Version of Record online: 30 MAY 2014 | DOI: 10.1002/anie.201402000

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      Click bait: An enzymatic system involving a clickable probe was developed for profiling the small-molecule substrates of glutathione S-transferases (GSTs). The GST mutant was paired with a clickable glutathione analogue to give a highly efficient enzyme–cofactor pair for labeling GST substrates. The conjugated GST substrates can then be biotinylated through click chemistry and subsequently enriched and then analyzed by LC–MS/MS.

    3. Low-Valent Uranium (1)

      Coordination and Redox Isomerization in the Reduction of a Uranium(III) Monoarene Complex (pages 7154–7157)

      Dr. Henry S. La Pierre, Dr. Hajime Kameo, MSc. Dominik P. Halter, Dr. Frank W. Heinemann and Prof. Dr. Karsten Meyer

      Version of Record online: 30 MAY 2014 | DOI: 10.1002/anie.201402048

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      U2 bites: Cyclic voltammetry scans of the uranium(III) complex [{(Ad,MeArO)3Mes}U] (1) revealed a reversible reduction at −2.495 V—the first electrochemical evidence for a formally divalent molecular uranium complex. Chemical reduction of 1 initiates redox isomerization and coordination to form a uranium hydride, and, upon addition of a crown ether, hydride insertion into the coordinated arene occurs.

    4. Low-Valent Uranium (2)

      Synthesis and Characterization of a Uranium(II) Monoarene Complex Supported by δ Backbonding (pages 7158–7162)

      Dr. Henry S. La Pierre, Dr. Andreas Scheurer, Dr. Frank W. Heinemann, Priv.-Doz. Dr. Wolfgang Hieringer and Prof. Dr. Karsten Meyer

      Version of Record online: 30 MAY 2014 | DOI: 10.1002/anie.201402050

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      U2 rocks: The molecular and electronic structure of a uranium(II) monoarene complex with a 5f 4 electronic configuration supported by δ backbonding was established experimentally by single-crystal X-ray diffraction, variable-temperature 1H NMR and X-band EPR spectroscopy, solution-state and solid-state magnetism studies, and optical absorption spectroscopy. The electronic structure of the complex was further investigated by DFT calculations.

    5. Cancer Nanotechnology

      Conjugated-Polyelectrolyte-Based Polyprodrug: Targeted and Image-Guided Photodynamic and Chemotherapy with On-Demand Drug Release upon Irradiation with a Single Light Source (pages 7163–7168)

      Dr. Youyong Yuan, Dr. Jie Liu and Prof. Dr. Bin Liu

      Version of Record online: 23 MAY 2014 | DOI: 10.1002/anie.201402189

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      Three in one: A theranostic nanoplatform based on a conjugated polyelectrolyte covalently linked to an anticancer drug (orange) through a linker (green) cleaved by reactive oxygen species (ROS) had functionalities for image, therapy, and on-demand drug release (see picture). An enhanced therapeutic effect was possible through combined photodynamic therapy and chemotherapy with ROS-triggered drug release upon illumination with a single light switch.

    6. Electrocatalysis

      In Situ Observation of Surface Species on Iridium Oxide Nanoparticles during the Oxygen Evolution Reaction (pages 7169–7172)

      Hernan G. Sanchez Casalongue, Dr. May Ling Ng, Dr. Sarp Kaya, Dr. Daniel Friebel, Dr. Hirohito Ogasawara and Dr. Anders Nilsson

      Version of Record online: 28 MAY 2014 | DOI: 10.1002/anie.201402311

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      The surface species of an iridium oxide electrocatalyst under oxygen evolution reaction (OER) conditions were probed by ambient-pressure X-ray photoelectron spectroscopy (APXPS). Under OER conditions, iridium undergoes a change in oxidation state from IrIV to IrV predominantly at the catalyst surface, indicating that the OER on iridium oxide occurs on a single iridium site, suggesting an OOH-mediated mechanism.

    7. Polymorphism

      Thermally Driven Polymorphic Transition Prompting a Naked-Eye-Detectable Bending and Straightening Motion of Single Crystals (pages 7173–7178)

      Tatsuya Shima, Dr. Takahiro Muraoka, Dr. Norihisa Hoshino, Prof. Tomoyuki Akutagawa, Dr. Yuka Kobayashi and Prof. Kazushi Kinbara

      Version of Record online: 30 MAY 2014 | DOI: 10.1002/anie.201402560

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      A rigorous workout: An amphiphile composed of two tetra(ethylene glycol) chains connecting ππ-stacking rigid aromatic units showed a reversible thermally driven single-crystal-to-single-crystal transition involving a bending and straightening motion on a macroscopic scale (see picture). The single-crystal motion occurs as a result of changes in the conformation and alignment of the molecules rather than bond formation/cleavage.

    8. Drug Design

      Preparation of Well-Defined Antibody–Drug Conjugates through Glycan Remodeling and Strain-Promoted Azide–Alkyne Cycloadditions (pages 7179–7182)

      Dr. Xiuru Li, Dr. Tao Fang and Prof. Dr. Geert-Jan Boons

      Version of Record online: 23 MAY 2014 | DOI: 10.1002/anie.201402606

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      Dressed to kill: Enzymatic remodeling of the glycans of cancer-targeting antibodies to include a sialic acid moiety modified with an azido function enables the site-specific attachment of cytotoxic drugs by strain-promoted azide–alkyne cycloaddition. An anti-CD22 antibody modified with doxorubicin (Dox) is shown to selectively target and kill lymphoma cells.

    9. Signaling Cascades | Hot Paper

      Signal Propagation in Multi-Layer DNAzyme Cascades Using Structured Chimeric Substrates (pages 7183–7187)

      Dr. Carl W. Brown III, Dr. Matthew R. Lakin, Eli K. Horwitz, M. Leigh Fanning, Hannah E. West, Prof. Darko Stefanovic and Prof. Steven W. Graves

      Version of Record online: 2 JUN 2014 | DOI: 10.1002/anie.201402691

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      Signaling between DNAzymes was achieved using a structured chimeric substrate (SCS) that releases a downstream activator after cleavage by an upstream DNAzyme. The SCS molecule can be activated by various upstream DNAzymes and coupled to DNA strand-displacement devices, and it is highly resistant to interference from background DNA. This work enables the rational design of synthetic regulatory networks, with potential applications in biodetection and theranostics.

    10. Zeotype Frameworks

      A 3D Aluminoborate Open Framework Interpenetrated by 2D Zinc–Amine Coordination-Polymer Networks in Its 11-Ring Channels (pages 7188–7191)

      Li Wei, Qi Wei, Dr. Zhi-En Lin, Qin Meng, Huan He, Bai-Feng Yang and Prof. Dr. Guo-Yu Yang

      Version of Record online: 30 MAY 2014 | DOI: 10.1002/anie.201402663

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      A union grounded in independence: An inorganic–organic hybrid solid, [Zn(NH2C3H6NH2)2][AlB5O10], combining the structural features of 3D open-framework inorganic solids and 2D zinc–amine coordination polymers was synthesized under solvothermal conditions with the coordination polymer in the pores of the aluminoborate (Zn purple, Al yellow, B5O10 green). The hybrid showed extensive luminescence and moderate second-harmonic-generation efficiency.

    11. Second Messenger Signaling

      Elucidating Diphosphoinositol Polyphosphate Function with Nonhydrolyzable Analogues (pages 7192–7197)

      Mingxuan Wu, Lucy S. Chong, Samanta Capolicchio, Dr. Henning J. Jessen, Dr. Adam C. Resnick and Dr. Dorothea Fiedler

      Version of Record online: 30 MAY 2014 | DOI: 10.1002/anie.201402905

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      Stable analogues of high-energy messengers: Bisphosphonate analogues of the diphosphoinositol polyphosphate (PP-IP) messengers are resistant to chemical and biochemical degradation. The compounds mimic the natural counterparts well when proteins are regulated allosterically by PP-IPs, but have an opposing effect in protein pyrophosphorylation. Thus, the compounds can be used to elucidate PP-IP signaling properties.

    12. Enzyme Catalysis

      Novel Product Chemistry from Mechanistic Analysis of ent-Copalyl Diphosphate Synthases from Plant Hormone Biosynthesis (pages 7198–7202)

      Kevin Potter, Jared Criswell, Dr. Jiachen Zi, Alisha Stubbs and Prof. Dr. Reuben J. Peters

      Version of Record online: 23 MAY 2014 | DOI: 10.1002/anie.201402911

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      Getting active: An active-site water molecule, coordinated by histidine and asparagine residues, serves as the catalytic base in all ent-copalyl diphosphate synthases (CPSs). When these residues are substituted by alanine, the mutant CPSs produce stereochemically novel ent-8-hydroxy-CPP. Given the requisite presence of CPSs in all land plants for gibberellin phytohormone biosynthesis, such plasticity presumably underlies the observed diversification of the resulting labdane-related diterpenoids.

    13. Cs+ Removal | Very Important Paper

      A Novel Vanadosilicate with Hexadeca-Coordinated Cs+ Ions as a Highly Effective Cs+ Remover (pages 7203–7208)

      Dr. Shuvo Jit Datta, Won Kyung Moon, Do Young Choi, Prof. Dr. In Chul Hwang and Prof. Dr. Kyung Byung Yoon

      Version of Record online: 22 MAY 2014 | DOI: 10.1002/anie.201402778

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      A novel vanadosilicate is an excellent remover of Cs+ ions from groundwater, seawater, and highly acidic or basic nuclear waste solutions. This material can therefore be used for the removal of radioactive 137Cs+ ions from contaminated water.

    14. [3+2] Cycloaddition

      [3+2] Cycloaddition of Propargylic Alcohols and α-Oxo Ketene Dithioacetals: Synthesis of Functionalized Cyclopentadienes and Further Application in a Diels–Alder Reaction (pages 7209–7213)

      Zhongxue Fang, Jianquan Liu, Prof. Qun Liu and Prof. Xihe Bi

      Version of Record online: 30 MAY 2014 | DOI: 10.1002/anie.201403014

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      2,5-Dialkylthio cyclopentadienes were prepared by the BF3⋅Et2O catalyzed regiospecific [3+2] cycloaddition of propargylic alcohols and α-oxo ketene dithioacetals in good to excellent yields. Furthermore, an unusual dethiolating Diels–Alder reaction of these cyclopentadienes with maleimides was discovered, which yielded novel fluorescent polycyclic compounds.

    15. Copper Hydrides

      Chinese Puzzle Molecule: A 15 Hydride, 28 Copper Atom Nanoball (pages 7214–7218)

      Dr. Alison J. Edwards, Dr. Rajendra S. Dhayal, Dr. Ping-Kuei Liao, Jian-Hong Liao, Dr. Ming-Hsi Chiang, Dr. Ross O. Piltz, Dr. Samia Kahlal, Prof. Jean-Yves Saillard and Prof. C. W. Liu

      Version of Record online: 6 MAY 2014 | DOI: 10.1002/anie.201403324

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      Rhombicuboctahedral nanoclusters: Two isostructural and concentric clusters [Cu28(H)15(S2CNR)12]PF6 (NR=NnPr2, aza-15-crown-5) are air- and moisture-stable and were prepared through a one-pot synthesis. The presence of capping, truncating, and interstitial hydrides within the metal framework was confirmed by single-crystal neutron diffraction and reproduced by DFT calculations.

    16. Synthetic Methods

      Palladium-Catalyzed Cascade Annulation To Construct Functionalized β- and γ-Lactones in Ionic Liquids (pages 7219–7222)

      Jianxiao Li, Wanfei Yang, Dr. Shaorong Yang, Liangbin Huang, Dr. Wanqing Wu, Yadong Sun and Prof. Dr. Huanfeng Jiang

      Version of Record online: 27 MAY 2014 | DOI: 10.1002/anie.201403341

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      Four in one: A highly efficient and mild palladium-catalyzed, one-pot, four-step cascade annulation has been developed to afford the title compounds in moderate to good yields with high regio- and diastereoselectivities in ionic liquids, thus making the transformation green and practical. In particular, this reaction provides a novel and convenient methodology for the construction of naturally occurring biologically active β- and γ-lactones.

    17. Nanoarray Catalysts

      Monolithically Integrated Spinel MxCo3−xO4 (M=Co, Ni, Zn) Nanoarray Catalysts: Scalable Synthesis and Cation Manipulation for Tunable Low-Temperature CH4 and CO Oxidation (pages 7223–7227)

      Zheng Ren, Venkatesh Botu, Sibo Wang, Yongtao Meng, Wenqiao Song, Dr. Yanbing Guo, Prof. Dr. Ramamurthy Ramprasad, Prof. Dr. Steven L. Suib and Prof. Dr. Pu-Xian Gao

      Version of Record online: 30 MAY 2014 | DOI: 10.1002/anie.201403461

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      Industrial-scale fabrication of spinel nanoarray monolithic catalysts is presented. The catalytic performance is tunable towards different low-temperature catalytic oxidation by rationally manipulated cation occupancy and concentration, which lead to controlled gas adsorption–desorption behavior and adjusted surface-oxygen defect population.

    18. Peptide Folding and Assembly

      Coordination-Driven Folding and Assembly of a Short Peptide into a Protein-like Two-Nanometer-Sized Channel (pages 7228–7232)

      Dr. Tomohisa Sawada, Asami Matsumoto and Prof. Dr. Makoto Fujita

      Version of Record online: 23 MAY 2014 | DOI: 10.1002/anie.201403506

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      Silver(I) coordination induces the folding and assembly processes of a short peptide ligand containing the Gly-Pro-Pro sequence in aqueous alcohol, giving rise to a single crystal composed of polyproline II helices. This peptide-folded porous crystal possesses two-nanometer-sized helical nanochannels, which efficiently take up anions, organic chiral molecules, and bio-oligomers.

    19. Metal Hydride Clusters

      Hydride Migration from a Triangular Face to a Tetrahedral Cavity in Tetranuclear Iron Carbonyl Clusters upon Coordination of [AuPPh3]+ Fragments (pages 7233–7237)

      Dr. Marco Bortoluzzi, Dr. Iacopo Ciabatti, Dr. Cristina Femoni, Dr. Mohammad Hayatifar, Prof. Maria Carmela Iapalucci, Prof. Giuliano Longoni and Prof. Stefano Zacchini

      Version of Record online: 21 MAY 2014 | DOI: 10.1002/anie.201403538

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      Caught in a trap: The first low-valent molecular metal cluster containing an interstitial four-coordinate hydride ion in a tetrahedral site has been obtained and fully characterized. Its formation proceeds via hydride migration from the surface to the tetrahedral cavity of the tetra-iron cage after addition of a [AuPPh3]+ fragment.

    20. Azido Interactions

      Solid-State Hierarchical Cyclodextrin-Based Supramolecular Polymer Constructed by Primary, Secondary, and Tertiary Azido Interactions (pages 7238–7242)

      Dr. Mickaël Ménand, Dr. Ségolène Adam de Beaumais, Lise-Marie Chamoreau, Dr. Etienne Derat, Dr. Sébastien Blanchard, Dr. Yongmin Zhang, Dr. Laurent Bouteiller and Prof. Matthieu Sollogoub

      Version of Record online: 27 MAY 2014 | DOI: 10.1002/anie.201403578

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      Self-assembled polymer: The crystallization of a di-azido-α-cyclodextrin revealed a polymeric self-assembly involving a variety of azido-type interactions. The crystal arrangement relies on the cooperativity of a primary azido inclusion, a secondary azido–azido interaction involving an unprecedented distribution of canonical forms, and a tertiary azido–hydrogen bonding array located in the groove of a CD-based polymeric helix.

    21. Supramolecular Chirality

      High Diastereoselection of a Dissymmetric Capsule by Chiral Guest Complexation (pages 7243–7247)

      Yuta Tsunoda, Katsunori Fukuta, Taisuke Imamura, Prof. Dr. Ryo Sekiya, Dr. Taniyuki Furuyama, Prof. Dr. Nagao Kobayashi and Prof. Dr. Takeharu Haino

      Version of Record online: 2 JUN 2014 | DOI: 10.1002/anie.201403721

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      Guests in a twist: Coordination-driven self-assembly of an achiral cavitand produced a dissymmetric capsule. Interconversion of the P and M helicities of the capsule was biased by the encapsulation of a chiral guest with remarkable diastereoselectivity. The absolute helicity of the diastereomeric complex was determined based on CD exciton coupling theory and DFT calculations.

    22. Planar Hexacoordinate Carbon

      Be2C Monolayer with Quasi-Planar Hexacoordinate Carbons: A Global Minimum Structure (pages 7248–7252)

      Prof. Dr. Yafei Li, Yunlong Liao and Prof. Dr. Zhongfang Chen

      Version of Record online: 12 MAY 2014 | DOI: 10.1002/anie.201403833

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      Promising material: In the two-dimensional Be2C monolayer, each carbon atom binds to six Be atoms forming a quasi-planar hexacoordinate carbon moiety (see structure; C black, Be green). Be2C monolayer has good stability and is the global minimum structure in 2D space. Further, it is semiconducting with a moderate direct band gap.

    23. Homogeneous Catalysis

      Deactivation of Cationic CuI and AuI Catalysts for A3 Coupling by CH2Cl2: Mechanistic Implications of the Formation of Neutral CuI and AuI Chlorides (pages 7253–7258)

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

      Version of Record online: 30 MAY 2014 | DOI: 10.1002/anie.201403973

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      Proceed with caution! Care should be exercised when using CH2Cl2 as a solvent for reactions in which amines are a reagent, since undesirable deactivation of cationic CuI and AuI catalysts to form the corresponding inactive neutral chloride complexes [LMCl] (M=Cu or Au) can occur as a result of the generation of hydrogen chloride in the medium. This phenomenon was studied on the basis of a Mannich three-component coupling reaction (see scheme).

    24. Supramolecular Sensors

      Supramolecular Luminescent Lanthanide Dimers for Fluoride Sequestering and Sensing (pages 7259–7263)

      Dr. Tao Liu, Dr. Aline Nonat, Dr. Maryline Beyler, Dr. Martín Regueiro-Figueroa, Dr. Katia Nchimi Nono, Dr. Olivier Jeannin, Dr. Franck Camerel, Dr. François Debaene, Dr. Sarah Cianférani-Sanglier, Prof. Raphaël Tripier, Dr. Carlos Platas-Iglesias and Dr. Loïc J. Charbonnière

      Version of Record online: 6 JUN 2014 | DOI: 10.1002/anie.201404847

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      Fluoride anions can be detected at the nanomolar level in aqueous solution with a luminescent europium complex that forms dimeric supramolecular assemblies. The fluoride-containing complexes are stabilized by a bridging Eu[BOND]F[BOND]Eu coordination mode, π–π stacking interactions, and a hydrogen-bonding network, which control the assembly of the two europium complexes around the fluoride anion.

    25. Supramolecular Hydrogels

      Two-Photon-Responsive Supramolecular Hydrogel for Controlling Materials Motion in Micrometer Space (pages 7264–7267)

      Tatsuyuki Yoshii, Dr. Masato Ikeda and Prof. Dr. Itaru Hamachi

      Version of Record online: 27 MAY 2014 | DOI: 10.1002/anie.201404158

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      Exciting developments: Fluidity inside a supramolecular hydrogel consisting of a nanofiber network has been controlled in a spatiotemporal manner by two-photon excitation. The off–on switching of the Brownian motion of nanobeads and the chemotaxis of bacteria by two-photon excitation was successfully demonstrated (see picture).

    26. Heterocycles | Very Important Paper

      Unlocking the N2 Selectivity of Benzotriazoles: Regiodivergent and Highly Selective Coupling of Benzotriazoles with Allenes (pages 7268–7271)

      Kun Xu, Niels Thieme and Prof. Dr. Bernhard Breit

      Version of Record online: 23 MAY 2014 | DOI: 10.1002/anie.201403682

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      Ligand control: Exceptionally high N2 and N1 selectivities have been achieved in the rhodium-catalyzed coupling of benzotriazoles with allenes by using DPEphos and JoSPOphos, respectively (see scheme). This method permits the atom-economic synthesis of valuable branched N2- and N1-allylated benzotriazole derivatives.

    27. C[BOND]N Activation

      Palladium-Catalyzed Insertion of an Allene into an Aminal: Aminomethylamination of Allenes by C[BOND]N Bond Activation (pages 7272–7276)

      Jianhua Hu, Yinjun Xie and Prof. Dr. Hanmin Huang

      Version of Record online: 30 MAY 2014 | DOI: 10.1002/anie.201403774

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      Break to link: The direct insertion of an allene into the C[BOND]N bond of an aminal in the presence of a palladium catalyst is described. This new method is concise and operationally simple and can be used for the atom-economic synthesis of a broad range of 1,3-diamines. The reaction involves cleavage of the C[BOND]N bond, formation of a π-allylpalladium intermediate, and nucleophilic addition.

    28. Rotational Spectroscopy

      Chirality Induction and Amplification in the 2,2,2-Trifluoroethanol⋅⋅⋅Propylene Oxide Adduct (pages 7277–7280)

      Javix Thomas, Prof. Dr. Wolfgang Jäger and Prof. Dr. Yunjie Xu

      Version of Record online: 4 JUN 2014 | DOI: 10.1002/anie.201403838

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      In the open: A broadband rotational spectroscopic investigation reveals that 2,2,2-trifluoroethanol (TFE)⋅⋅⋅propylene oxide (PO) exhibits noticeable chirality amplification: g+ TFE⋅⋅⋅S-PO was found to be favored over that of g− TFE⋅⋅⋅S-PO by a factor of 2.8 at 60 K. All the observed TFE⋅⋅PO conformers take on the open geometry, in contrast to 2-fluoroethanol⋅⋅⋅PO which prefers the closed form. Perfluorination at CH3 increases the binding energy of TFE⋅⋅⋅PO by 70 % over its ethanol counterpart.

    29. Oxygen Evolution

      Graphitic Carbon Nitride Nanosheet–Carbon Nanotube Three-Dimensional Porous Composites as High-Performance Oxygen Evolution Electrocatalysts (pages 7281–7285)

      Dr. Tian Yi Ma, Prof. Sheng Dai, Prof. Mietek Jaroniec and Prof. Shi Zhang Qiao

      Version of Record online: 2 JUN 2014 | DOI: 10.1002/anie.201403946

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      Combining C and N to make O: 3D porous graphitic carbon nitride nanosheet–carbon nanotube composites have been synthesized through a spontaneous assembly process. The high nitrogen content, enhanced electron conductivity, and improved mass transport result in excellent catalytic oxygen evolution activity and strong durability, superior to those reported for other nonmetal catalysts and noble-metal catalysts (see figure; OER: oxygen evolution reaction).

    30. Natural Product Synthesis

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      Total Synthesis of Jiadifenolide (pages 7286–7289)

      Prof. Dr. Ian Paterson, Mengyang Xuan and Dr. Stephen M. Dalby

      Version of Record online: 23 MAY 2014 | DOI: 10.1002/anie.201404224

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      Synthetic adventure: The total synthesis of the pentacyclic sesquiterpenoid jiadifenolide, a potent neurite outgrowth promoter, is reported. The synthesis showcases an adventurous samarium-mediated cyclization reaction to establish the ABC-tricyclic core and adjacent quaternary stereocenters. Late-stage oxidation of a pendant vinyl group completes the highly stereocontrolled assembly of this intricate structure.

    31. Ni-Catalyzed C[BOND]C Coupling | Very Important Paper

      Carbon–Carbon Cross-Coupling Reactions Catalyzed by a Two-Coordinate Nickel(II)–Bis(amido) Complex via Observable NiI, NiII, and NiIII Intermediates (pages 7290–7294)

      Michael I. Lipschutz and Prof. T. Don Tilley

      Version of Record online: 30 MAY 2014 | DOI: 10.1002/anie.201404577

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      Cross-examination: The C[BOND]C coupling of aryl halides with Grignard reagents in the presence of a two-coordinate nickel complex has been identified and evaluated mechanistically. A NiIII–alkyl species was isolated and fully characterized and compelling experimental evidence was found of the role played by this species as well as those of other key NiI and NiII intermediates in the catalytic cycle (see scheme, DIPP=2,6-diisopropylphenyl).

    32. Photoelectrochemistry

      A Tantalum Nitride Photoanode Modified with a Hole-Storage Layer for Highly Stable Solar Water Splitting (pages 7295–7299)

      Guiji Liu, Dr. Jingying Shi, Prof. Fuxiang Zhang, Zheng Chen, Jingfeng Han, Chunmei Ding, Shanshan Chen, Zhiliang Wang, Prof. Hongxian Han and Prof. Can Li

      Version of Record online: 30 MAY 2014 | DOI: 10.1002/anie.201404697

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      The presence of a ferrihydrite layer allows stable water oxidation at the Co3O4/ferrihydrite/Ta3N5 photoanode for at least 6 h. This is the Ta3N5-based photoanode that is the most durable against photocorrosion reported to date. The role of the ferrihydrite layer is a hole-storage layer, increasing the hole-storage capacity and suppressing photocorrosion of Ta3N5 electrode.

    33. Chiral Sulfilimines

      Rhodium-Catalyzed Stereoselective Amination of Thioethers with N-Mesyloxycarbamates: DMAP and Bis(DMAP)CH2Cl2 as Key Additives (pages 7300–7304)

      Prof. Dr. Hélène Lebel, Henri Piras and Johan Bartholoméüs

      Version of Record online: 30 MAY 2014 | DOI: 10.1002/anie.201402961

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      The select committee: A mixture of 4-dimethylaminopyridine (DMAP) and bis(DMAP)CH2Cl2 proved pivotal in achieving high selectivity in the Rh-catalyzed intermolecular amination of thioethers with a readily available chiral N-mesyloxycarbamate to produce sulfilimines in excellent yields. Mechanistic studies suggest a RhII-RhIII complex to be the catalytically active species.

    34. Photocatalysis

      Visible-Light-Induced Electron Transport from Small to Large Nanoparticles in Bimodal Gold Nanoparticle-Loaded Titanium(IV) Oxide (pages 7305–7309)

      Dr. Shin-ichi Naya, Tadahiro Niwa, Takahiro Kume and Prof. Dr. Hiroaki Tada

      Version of Record online: 26 MAY 2014 | DOI: 10.1002/anie.201402939

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      Visible-light-induced electron transport: Visible-light irradiation of TiO2-supported gold nanoparticles (NPs) with a bimodal size distribution (BM-Au/TiO2) gives rise to long-range electron transport from about 14 small NPs to one large Au NP through the conduction band of TiO2. As a result of the enhancement of the charge separation, BM-Au/TiO2 exhibits a high level of visible-light activity for the synthesis of azobenzenes (see picture) from nitrobenzenes.

    35. Biomass Conversion

      Catalytic Ethanolysis of Kraft Lignin into High-Value Small-Molecular Chemicals over a Nanostructured α-Molybdenum Carbide Catalyst (pages 7310–7315)

      Rui Ma, Wenyue Hao, Xiaolei Ma, Ye Tian and Prof. Yongdan Li

      Version of Record online: 2 JUN 2014 | DOI: 10.1002/anie.201402752

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      Krafty upgrade of a waste product: Kraft lignin was fully depolymerized into C6–C10 liquid products (see scheme) over a nanostructured α-molybdenum carbide catalyst in supercritical ethanol. In this process, which can be regarded as a fundamental finding for the upgrade of Kraft lignin to bio-oils under mild conditions, lignin fragments are rapidly stabilized with ethanol on the surface of the catalyst.

    36. Nanocluster

      Magnetic and Optoelectronic Properties of Gold Nanocluster–Thiophene Assembly (pages 7316–7319)

      Dr. Wei Qin, Jessica Lohrman and Prof. Shenqiang Ren

      Version of Record online: 22 MAY 2014 | DOI: 10.1002/anie.201402685

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      Nanohybrids consisting of Au nanocluster and polythiophene nanowire assemblies (see picture) exhibit unique thermal-responsive optical behaviors and charge-transfer controlled magnetic and optoelectronic properties. The Au nanoclusters enhance photoabsorption and conductivity, leading to an increase of power conversion efficiency by 14 %.

    37. Amine Synthesis

      Phosphine- and Hydrogen-Free: Highly Regioselective Ruthenium-Catalyzed Hydroaminomethylation of Olefins (pages 7320–7323)

      Dr. Samet Gülak, Lipeng Wu, Dr. Qiang Liu, Prof. Dr. Robert Franke, Dr. Ralf Jackstell and Prof. Dr. Matthias Beller

      Version of Record online: 23 MAY 2014 | DOI: 10.1002/anie.201402368

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      HAM it up: A highly regioselective ruthenium-catalyzed synthesis of amines, through hydroaminomethylation (HAM), is reported. This novel procedure is practical (P-ligand-free, one pot) and economic (low catalyst loading and inexpensive metal). Bulk industrial as well as functionalized olefins give the corresponding tertiary amines in high yields (up to 92 %) with excellent regioselectivities (n/iso>99:1) and full chemoselectivity.

    38. Organocatalysis

      Organocatalytic Oxidative Annulation of Benzamide Derivatives with Alkynes (pages 7324–7327)

      Srimanta Manna and Dr. Andrey P. Antonchick

      Version of Record online: 21 MAY 2014 | DOI: 10.1002/anie.201404222

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      Annulation without hesitation: N-alkoxybenzamides convert into isoquinolones smoothly and rapidly under organocatalytic conditions. The annulation of unsymmetrical diarylacetylenes proceeds with a high regioselectivity. The transformation is based on the hypervalent-iodine mediated generation of nitrenium ions.

    39. Natural Product Synthesis

      α- and β-Lipomycin: Total Syntheses by Sequential Stille Couplings and Assignment of the Absolute Configuration of All Stereogenic Centers (pages 7328–7334)

      Dr. Max L. Hofferberth and Prof. Dr. Reinhard Brückner

      Version of Record online: 4 JUN 2014 | DOI: 10.1002/anie.201402255

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      Making doubly sure: 40 years ago the structures of α-lipomycin and its aglycon β-lipomycin were determined except for the configurations of the side-chain stereocenters. All of the relevant β-lipomycin candidates have now been synthesized. The optical rotation of the (12R,13S) isomer matched that of the natural product. The (12R,13S)-configured D-digitoxide was synthesized too and identified as α-lipomycin.

    40. Natural Product Structures

      The Structure Elucidation and Total Synthesis of β-Lipomycin (pages 7335–7338)

      Dr. Olaf Hartmann and Prof. Dr. Markus Kalesse

      Version of Record online: 21 MAY 2014 | DOI: 10.1002/anie.201402259

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      Peekaboo with stereocenters: The hidden configuration of natural products can be uncovered using a statistical model to deduce unknown configurations from amino acid sequences of ketoreductases. The synthesis of β-lipomycin finally confirms the validity of this method in particular for chiral centers in α-position.

    41. Molecular Computing

      Sugar-based Molecular Computing by Material Implication (pages 7339–7343)

      Martin Elstner, Jörg Axthelm and Prof.Dr. Alexander Schiller

      Version of Record online: 12 JUN 2014 | DOI: 10.1002/anie.201403769

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      Logic gates with sugar and light: A molecular IMP (implication function) gate can be constructed with a boronic acid sugar probe which gives a fluorescent signal as an output. An external wiring algorithm translates the fluorescent output from one gate into a chemical input for the next gate on microtiter plates. This process is demonstrated on a four-bit full adder.

    42. Oxide Ion Conductor | Hot Paper

      A Metallic Room-Temperature Oxide Ion Conductor (pages 7344–7348)

      Martin Heise, Bertold Rasche, Dr. Anna Isaeva, Dr. Alexey I. Baranov, Prof. Dr. Michael Ruck, Konrad Schäfer, Prof. Dr. Rainer Pöttgen, Jens-Peter Eufinger and Prof. Dr. Jürgen Janek

      Version of Record online: 27 MAY 2014 | DOI: 10.1002/anie.201402244

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      Oxygen topochemistry: Nanoparticles of Bi3Ir, a hitherto uncharacterized intermetallic compound, reversibly intercalate oxygen from air at room temperature. In the resulting metallic suboxide, the intermetallic building units are preserved. The activation energy for oxide diffusion is one order of magnitude smaller than that in any known material. Bi3IrOx is the first metallic oxide ion conductor and also the first that operates at room temperature.

    43. Indole Synthesis

      Indole Synthesis Based On A Modified Koser Reagent (pages 7349–7353)

      Laura Fra, Dr. Alba Millán, Dr. José A. Souto and Prof. Dr. Kilian Muñiz

      Version of Record online: 28 MAY 2014 | DOI: 10.1002/anie.201402661

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      Convenient route to indole: A fast, productive, and operationally simple indole synthesis was developed. The oxidative cyclization of 2-vinyl anilines with iodosobenzene and the sterically congested aryl sulfonic acid 1 provides an efficient and convenient access to the indole core (see scheme; Cbz=benzyloxycarbonyl).

    44. Protein–Protein Interactions | Hot Paper

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      In Vitro Reconstitution of a Cellular Phase-Transition Process that Involves the mRNA Decapping Machinery (pages 7354–7359)

      Simon A. Fromm, Julia Kamenz, Erik R. Nöldeke, Ancilla Neu, Georg Zocher and Dr. Remco Sprangers

      Version of Record online: 26 MAY 2014 | DOI: 10.1002/anie.201402885

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      In phase: In vivo, components of the mRNA decay machinery can undergo a phase transition to form P-bodies. This spontaneous cellular clustering process was reconstituted using purified proteins. Intermolecular contacts between the Edc3 LSm domain and helical leucine-rich motifs in Dcp2 and Pdc1 form the backbone of the interaction network.

    45. Neutral Boron Radicals

      Isolation of a Neutral Boron-Containing Radical Stabilized by a Cyclic (Alkyl)(Amino)Carbene (pages 7360–7363)

      Dr. Philipp Bissinger, Prof. Dr. Holger Braunschweig, Dr. Alexander Damme, Dr. Ivo Krummenacher, Dr. Ashwini K. Phukan, Dr. Krzysztof Radacki and Shun Sugawara

      Version of Record online: 10 JUN 2014 | DOI: 10.1002/anie.201403514

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      Neutral boron radicals: Reduction of dihaloborane adducts stabilized by a cyclic (alkyl)(amino)carbene leads to the isolation of neutral radicals with a boryl unit. The structure of a duryl derivative was elucidated by X-ray analysis (see picture; duryl=2,3,5,6-tetramethylphenyl) and this radical was found to be highly stable. DFT calculations revealed that the species showed the largest spin density at boron compared to other isolated boryl radicals.

    46. Intrinsically Disordered Proteins | Hot Paper

      Mapping Multivalency and Differential Affinities within Large Intrinsically Disordered Protein Complexes with Segmental Motion Analysis (pages 7364–7367)

      Dr. Sigrid Milles and Dr. Edward A. Lemke

      Version of Record online: 4 JUN 2014 | DOI: 10.1002/anie.201403694

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      Flexible backbones: A combined fluorescence correlation and time-resolved polarization spectroscopy approach was used to study differential binding within large and disordered protein complexes with multivalent interactions. The differential segmental backbone mobility of a disordered nucleoporin in complex with transport receptors was detected. Local binding preferences were identified within the disordered protein which range over several orders of magnitude.

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