Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 12

March 17, 2014

Volume 53, Issue 12

Pages 3035–3279

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Review
    12. Communications
    13. And Finally
    1. You have free access to this content
      Cover Picture: Monitoring Conformational Changes in the NDM-1 Metallo-β-lactamase by 19F NMR Spectroscopy (Angew. Chem. Int. Ed. 12/2014) (page 3035)

      Anna M. Rydzik, Jürgen Brem, Sander S. van Berkel, Inga Pfeffer, Anne Makena, Dr. Timothy D. W. Claridge and Prof. Christopher J. Schofield

      Version of Record online: 3 MAR 2014 | DOI: 10.1002/anie.201401104

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      Increasing antibiotic resistance is a global health concern. Metallo-β-lactamases catalyze the hydrolysis of almost all β-lactam antibiotics. T. D. W. Claridge, C. J. Schofield et al. show in their Communication on page 3129 ff. how 19F NMR spectroscopy can be used to investigate the binding mode of inhibitors to the New Delhi Metallo-β-lactamase I (NDM-1). By labeling an active-site loop with 19F, changes in the local chemical environment caused by inhibitor binding can be readily monitored by NMR spectroscopy.

    2. You have free access to this content
      Inside Cover: The Topochemical Pseudomorphosis of a Chloride into a Bismuthide (Angew. Chem. Int. Ed. 12/2014) (page 3036)

      Martin Kaiser, Bertold Rasche and Prof. Dr. Michael Ruck

      Version of Record online: 3 MAR 2014 | DOI: 10.1002/anie.201401088

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      Although apparently trapped in the intermetallic framework of Bi12Rh3Cl2, the Cl ions can be replaced quantitatively by Bi atoms under mild conditions to yield the metastable intermetallic phase Bi14Rh3. M. Ruck et al. show in their Communication on page 3254 ff. that this transport of ions must occur through the seemingly dense framework. The unexpected flexibility of the intermetallic network of edge-sharing [RhBi8] cubes and antiprisms allows an unusual breathing mode to open large diffusion paths that enable efficient mass transport.

    3. You have free access to this content
      Inside Back Cover: Size-Selective Complexation and Extraction of Endohedral Metallofullerenes with Cycloparaphenylene (Angew. Chem. Int. Ed. 12/2014) (page 3281)

      Yusuke Nakanishi, Dr. Haruka Omachi, Sanae Matsuura, Prof. Dr. Yasumitsu Miyata, Prof. Dr. Ryo Kitaura, Prof. Dr. Yasutomo Segawa, Prof. Dr. Kenichiro Itami and Prof. Dr. Hisanori Shinohara

      Version of Record online: 3 MAR 2014 | DOI: 10.1002/anie.201401082

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      A new strategy for the nonchromatographic extraction of metallofullerenes from solutions of arc-processed raw soot is described by K. Itami, H. Shinohara et al. in their Communication on page 3102 ff. This method is based on the size-selective complexation with commercially available cycloparaphenylene (CPP). For example, Gd@C82 can be selectively extracted from a fullerene mixture by the addition of [11]CPP.

    4. You have free access to this content
      Back Cover: Engineering of P450pyr Hydroxylase for the Highly Regio- and Enantioselective Subterminal Hydroxylation of Alkanes (Angew. Chem. Int. Ed. 12/2014) (page 3282)

      Yi Yang, Dr. Ji Liu and Prof. Dr. Zhi Li

      Version of Record online: 24 FEB 2014 | DOI: 10.1002/anie.201401084

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      P450 enzymes that were obtained by the directed evolution of terminal-selective P450pyr hydroxylase enabled the first highly regio- and enantioselective subterminal hydroxylation of an alkane at a non-activated carbon atom, as described by Z. Li and co-workers in their Communication on page 3120 ff. The engineered P450 enzymes are useful catalysts for the regio- and stereoselective functionalization of alkanes and the preparation of enantiopure alcohols.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Review
    12. Communications
    13. And Finally
  3. Corrigendum

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Review
    12. Communications
    13. And Finally
    1. You have free access to this content
      Corrigendum: Studying 18 MDa Virus Assemblies with Native Mass Spectrometry (page 3051)

      Joost Snijder, Dr. Rebecca J. Rose, Dr. David Veesler, Prof. Dr. John E. Johnson and Prof. Dr. Albert J. R. Heck

      Version of Record online: 14 MAR 2014 | DOI: 10.1002/anie.201400943

      This article corrects:

      Studying 18 MDa Virus Assemblies with Native Mass Spectrometry1

      Vol. 52, Issue 14, 4020–4023, Version of Record online: 28 FEB 2013

  4. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Review
    12. Communications
    13. And Finally
  5. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Review
    12. Communications
    13. And Finally
    1. Burkhard Luy (page 3058)

      Version of Record online: 20 JAN 2014 | DOI: 10.1002/anie.201310223

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      “I can never resist a piece of good chocolate. My favorite author (fiction) is Sir Arthur Conan Doyle …” This and more about Burkhard Luy can be found on page 3058.

  6. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Review
    12. Communications
    13. And Finally
  7. Obituary

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Review
    12. Communications
    13. And Finally
    1. Frederick Sanger (1918–2013) (page 3060)

      Alan Coulson

      Version of Record online: 3 FEB 2014 | DOI: 10.1002/anie.201310781

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  8. Book Reviews

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Review
    12. Communications
    13. And Finally
    1. Does Science Need a Global Language? By Scott L. Montgomery. (pages 3061–3062)

      Henning Hopf

      Version of Record online: 13 JAN 2014 | DOI: 10.1002/anie.201309883

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      The University of Chicago Press, Chicago, 2013. 226 pp., hardcover, $ 22.50.—ISBN 978-0226535036

    2. Antibiotics. Targets, Mechanisms and Resistance. Edited by Claudio O. Gualerzi, Letizia Brandi, Attilio Fabbretti, and Cynthia L. Pon. (page 3062)

      Klaus-Peter Koller

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/anie.201400593

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      Wiley-VCH, Weinheim, 2013. 576 pp., hardcover, € 149.00.—ISBN 978-527333059

  9. Highlights

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Review
    12. Communications
    13. And Finally
    1. Cluster Compounds

      Nanoscale Molecular Silver Cluster Compounds in Gram Quantities (pages 3064–3066)

      Prof. Dr. Andreas Schnepf and Prof. Dr. Hansgeorg Schnöckel

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201310158

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      All that′s nano is not gold: Definite, crystalline molecular compounds of noble metals have been known for gold for the last few years. Now a simple synthesis of a nanoscale silver cluster compound containing [Ag44(S-C6H4COOH)30]4− ions has been found leading to gram scales quantities. Synthetic, structural, and bonding aspects of this novel compound are discussed in the context of metalloid clusters in general.

    2. Enzyme Catalysis

      Hydroxy Functionalization of Non-Activated C[BOND]H and C[DOUBLE BOND]C Bonds: New Perspectives for the Synthesis of Alcohols through Biocatalytic Processes (pages 3067–3069)

      Prof. Dr. Harald Gröger

      Version of Record online: 3 MAR 2014 | DOI: 10.1002/anie.201308556

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      New perspectives through enzymes: Recent breakthroughs have been achieved in the selective hydroxy functionalization of non-activated C[BOND]H and C[DOUBLE BOND]C bonds. Enzymes turned out to be suitable catalysts for the ω-hydroxylation of (substituted) alkanes and regioselective hydroxylation of aromatic hydrocarbons with atmospheric oxygen as the oxidant, and the asymmetric addition of water to non-activated alkenes.

  10. Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Review
    12. Communications
    13. And Finally
    1. Biocatalysis

      New Generation of Biocatalysts for Organic Synthesis (pages 3070–3095)

      Bettina M. Nestl, Stephan C. Hammer, Bernd A. Nebel and Prof. Dr. Bernhard Hauer

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201302195

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      A dash of BIO-catalyst: A new generation of biocatalysts has entered modern organic synthesis. Recent advances in enzyme catalysis for the synthesis of challenging chemicals are presented in this Review.

  11. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Review
    12. Communications
    13. And Finally
    1. Antiaromatic Batteries

      An Antiaromatic Electrode-Active Material Enabling High Capacity and Stable Performance of Rechargeable Batteries (pages 3096–3101)

      Prof. Dr. Ji-Young Shin, Dr. Tetsuya Yamada, Prof. Dr. Hirofumi Yoshikawa, Prof. Dr. Kunio Awaga and Prof. Dr. Hiroshi Shinokubo

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/anie.201310374

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      The balance of power: A discharge capacity of greater than 200 mA h g−1 over 100 charge/discharge cycles was found for a rechargeable battery with an antiaromatic norcorrole NiII complex (NiNC) as a cathode-active material and a Li metal anode. The bipolar redox property of NiNC also enabled the construction of a Li metal free rechargeable battery with high discharge capacity (see scheme) and good cycle performance.

    2. Metallofullerenes

      Size-Selective Complexation and Extraction of Endohedral Metallofullerenes with Cycloparaphenylene (pages 3102–3106)

      Yusuke Nakanishi, Dr. Haruka Omachi, Sanae Matsuura, Prof. Dr. Yasumitsu Miyata, Prof. Dr. Ryo Kitaura, Prof. Dr. Yasutomo Segawa, Prof. Dr. Kenichiro Itami and Prof. Dr. Hisanori Shinohara

      Version of Record online: 24 FEB 2014 | DOI: 10.1002/anie.201311268

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      Complexation: A new strategy for the non-chromatographic extraction of metallofullerenes from solutions of arc-processed raw soot is based on the size-selective complexation with cycloparaphenylene (CPP). [11]CPP has a high affinity for Mx@C82 (x=1, 2); for example, Gd@C82 can be selectively extracted from a fullerene mixture by the addition of [11]CPP.

    3. Natural Product Synthesis

      Total Syntheses of Secalonic Acids A and D (pages 3107–3110)

      Tian Qin and Prof. Dr. John A. Porco Jr.

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201311260

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      It takes two: Concise syntheses of the natural products secalonic acids A and D using copper(I)-mediated dimerization of complex aryl stannane monomers to construct the requisite 2,2′-biphenol linkage are reported. Highly efficient kinetic resolution of the monomeric tetrahydroxanthone core structures was achieved using homobenzotetramisole catalysis. DMA=N,N-dimethyl acetamide, MOM=methoxymethyl.

    4. Square-Planar Cobalt(II)

      Two-Orbital Three-Electron Stabilizing Interaction for Direct Co2+[BOND]As3+ Bonds involving Square-Planar CoO4 in BaCoAs2O5 (pages 3111–3114)

      Rénald David, Houria Kabbour, Alain Pautrat, Nadia Touati, Myung-Hwan Whangbo and Olivier Mentré

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201311183

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      As on a plane: BaCoAs2O5 exhibits nearly square-planar Co2+O4 units that possess direct Co2+[BOND]As3+ bonds (2.51 Å). Owing to the high-spin character of the Co2+ ion, the As[BOND]Co bond is stabilized by a two-orbital three-electron interaction between the filled dz2 Co2+ orbital and the lone pair (E) of As3+.

    5. Total Synthesis

      C[BOND]H Bond Arylation in the Synthesis of Aryltetralin Lignans: A Short Total Synthesis of Podophyllotoxin (pages 3115–3119)

      Chi P. Ting and Prof. Dr. Thomas J. Maimone

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201311112

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      Testing a new tactic: In a concise synthesis of podophyllotoxin with a crucial palladium-catalyzed arylation step, subtle conformational effects govern reductive elimination pathways from the high-valent palladium center. This route to aryltetralin lignan derivatives may be of interest in drug discovery.

    6. C[BOND]H activation

      Engineering of P450pyr Hydroxylase for the Highly Regio- and Enantioselective Subterminal Hydroxylation of Alkanes (pages 3120–3124)

      Yi Yang, Dr. Ji Liu and Prof. Dr. Zhi Li

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/anie.201311091

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      Get a handle on it: Highly regio- and enantioselective subterminal hydroxylation of n-octane and propylbenzene was observed with P450 enzymes obtained by the directed evolution of terminal-selective P450pyr hydroxylase (see scheme). The engineered enzymes with their fully altered selectivities are useful for the functionalization of alkanes and the preparation of enantiomerically pure alcohols.

    7. Hypervalent Iodine Reagents

      Structural Reevaluation of the Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation Supported by the Crystalline Sponge Method for X-ray Analysis (pages 3125–3128)

      Ekaterina V. Vinogradova, Dr. Peter Müller and Prof. Dr. Stephen L. Buchwald

      Version of Record online: 14 FEB 2014 | DOI: 10.1002/anie.201310897

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      Not-so-hypervalent iodine: Studies of several benziodoxole thiolate derivatives revealed that these species lack the hypervalent iodine motif, instead adopting a thioperoxide configuration. Crystallographic analysis of a liquid trifluoromethylthiolation reagent trapped inside a metal–organic framework provided direct structural proof for the observed phenomenon. These thioperoxide reagents were also shown to be reactive in electrophilic substitution reactions.

    8. Metallo-β-lactamases

      You have full text access to this OnlineOpen article
      Monitoring Conformational Changes in the NDM-1 Metallo-β-lactamase by 19F NMR Spectroscopy (pages 3129–3133)

      Anna M. Rydzik, Jürgen Brem, Sander S. van Berkel, Inga Pfeffer, Anne Makena, Dr. Timothy D. W. Claridge and Prof. Christopher J. Schofield

      Version of Record online: 24 FEB 2014 | DOI: 10.1002/anie.201310866

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      19Follow the moves: 19F NMR spectroscopy is used to monitor active-site loop movements in the New Delhi metallo-β-lactamase (NDM-1) following site-selective cysteine S-alkylation with CH2COCF3. The method discriminates between types of inhibition and enables determination of binding constants and will be useful in identifying inhibitors of clinically important metallo-β-lactamases.

    9. Porous Materials

      Mesoporous Prussian Blue Analogues: Template-Free Synthesis and Sodium-Ion Battery Applications (pages 3134–3137)

      Dr. Yanfeng Yue, Andrew J. Binder, Dr. Bingkun Guo, Dr. Zhiyong Zhang, Dr. Zhen-An Qiao, Chengcheng Tian and Prof.Dr. Sheng Dai

      Version of Record online: 14 FEB 2014 | DOI: 10.1002/anie.201310679

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      Blue, blue, electric blue: Porous Prussian blue analogues with tailorable surface area and pore structure were synthesized through a facile template-free method at room temperature. This methodology could provide an alternative to the hard or soft templating methods for fabricating crystalline mesoporous materials. As cathodes for sodium-ion batteries, these porous Prussian blue analogues showed reversible capacity and excellent cycle stability.

    10. Polymersomes

      Concurrent Block Copolymer Polymersome Stabilization and Bilayer Permeabilization by Stimuli-Regulated “Traceless” Crosslinking (pages 3138–3142)

      Xiaorui Wang, Guhuan Liu, Dr. Jinming Hu, Prof. Dr. Guoying Zhang and Prof. Dr. Shiyong Liu

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201310589

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      Two processes in one: A stimuli-triggered crosslinking strategy was developed to concurrently crosslink and permeabilize block copolymer assemblies. Upon self-assembling into polymersomes (see picture), light-triggered self-immolative decaging reactions release primary amine moieties and lead to extensive amidation reactions.

    11. Ionic Liquids

      Charge-Scaling Effect in Ionic Liquids from the Charge-Density Analysis of N,N′-Dimethylimidazolium Methylsulfate (pages 3143–3146)

      Dr. Witali Beichel, Dr. Nils Trapp, Dipl.-Phys. Christoph Hauf, Dipl.-Ing. Oliver Kohler, Dr. Georg Eickerling, Prof. Dr. Wolfgang Scherer and Prof. Dr. Ingo Krossing

      Version of Record online: 20 FEB 2014 | DOI: 10.1002/anie.201308760

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      In charge? The (down-)scaling of partial charges in non-polarizable force fields is commonly applied for the simulation of ionic liquids. Analyses of charge densities, employing the quantum theory of atoms in molecules, on the prototype ionic liquid [C1MIM][C1SO4] are shown to provide an experimental justification for such a treatment.

    12. Nanoparticles by Spray Ionization

      Synthesis and Catalytic Reactions of Nanoparticles formed by Electrospray Ionization of Coinage Metals (pages 3147–3150)

      Anyin Li, Qingjie Luo, Prof. So-Jung Park and Prof. R. Graham Cooks

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/anie.201309193

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      High catalytic activity: Copper, silver, and gold solids are ionized to the +1 oxidation state ions by electrospray in acetonitrile (ACN) as an anhydrous organic solvent. Collection of the solvated ions leads to formation of nanoparticles that serve as catalysts for bulk reactions, for example the reduction of p-nitrophenol by NaBH4.

    13. Perovskite Solar Cells

      Mixed-Organic-Cation Perovskite Photovoltaics for Enhanced Solar-Light Harvesting (pages 3151–3157)

      Norman Pellet, Dr. Peng Gao, Dr. Giuliano Gregori, Dr. Tae-Youl Yang, Dr. Mohammad K. Nazeeruddin, Prof. Joachim Maier and Prof. Michael Grätzel

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/anie.201309361

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      A productive partnership: Perovskite solar devices with mixed organic cations could outperform the standard methylammonium lead iodide pigment owing to extended light absorption and a higher carrier-diffusion length. Thus, the best optoelectronic features of methylammonium and formamidinium cations were combined in a perovskite solar cell with a striking 14.9 % power-conversion efficiency (red curve: in simulated sunlight; blue curve: in the dark).

    14. Radical Cyclization

      Transition from π Radicals to σ Radicals: Substituent-Tuned Cyclization of Hydrazonyl Radicals (pages 3158–3162)

      Xiao-Yong Duan, Neng-Neng Zhou, Dr. Ran Fang, Xiu-Long Yang, Prof. Dr. Wei Yu and Prof. Dr. Bing Han

      Version of Record online: 14 FEB 2014 | DOI: 10.1002/anie.201309918

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      Time for a radical career change? Known for their π character, hydrazonyl radicals can be tuned to act as σ radicals with the spin density delocalized on both nitrogen atoms by attaching a trifluoroacetyl or trichloroacetyl group to the N1 atom. The hydrazonyl σ radicals derived from the corresponding N-acyl-substituted β,γ- and γ,δ-unsaturated hydrazones underwent C[BOND]N1 and C[BOND]N2 bond-forming 5-exo-trig cyclization, respectively (see scheme).

    15. Molecular Diagnostics

      Accurate Zygote-Specific Discrimination of Single-Nucleotide Polymorphisms Using Microfluidic Electrochemical DNA Melting Curves (pages 3163–3167)

      Allen H. J. Yang, Kuangwen Hsieh, Adriana S. Patterson, B. Scott Ferguson, Michael Eisenstein, Prof. Kevin W. Plaxco and Prof. H. Tom Soh

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201310059

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      Rapid DNA identification: A novel microfluidic electrochemical system for the detection of single-nucleotide polymorphisms (SNPs) uses surface-immobilized DNA probes to accurately discriminate homozygous and heterozygous genotypes using real-time melting-curve analysis. Two clinically relevant SNPs in the apolipoprotein E gene were characterized and all six possible ApoE allele combinations were distinguished.

    16. Fluorescent Heterocycles

      Palladium-Catalyzed C[BOND]H Fluorosilylation of 2-Phenylpyridines: Synthesis of Silafluorene Equivalents (pages 3168–3172)

      Dr. Qing Xiao, Dr. Xiangtai Meng, Prof. Dr. Motomu Kanai and Prof. Dr. Yoichiro Kuninobu

      Version of Record online: 14 MAR 2014 | DOI: 10.1002/anie.201310293

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      Treatment of 2-phenylpyridines with amino(1,3,2-dioxaborolan-2-yl)diphenylsilane produced fluorosilylated 2-phenylpyridines in good to excellent yields under palladium catalysis. This reaction is the first example of C[BOND]H fluorosilylation. A Lewis acid–base interaction exists between the silicon and nitrogen atoms, and the obtained fluorosilylated products can be regarded as silafluorene equivalents.

    17. Magnesium Batteries

      You have full text access to this OnlineOpen article
      Boron Clusters as Highly Stable Magnesium-Battery Electrolytes (pages 3173–3177)

      Tyler J. Carter, Dr. Rana Mohtadi, Dr. Timothy S. Arthur, Dr. Fuminori Mizuno, Dr. Ruigang Zhang, Dr. Soichi Shirai and Dr. Jeff W. Kampf

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201310317

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      A b(o)rilliant improvement: An electrolyte incorporating an unprecedented magnesium-centered complex anion was developed for use in rechargeable magnesium batteries. The carboranyl magnesium halide (see structure; B purple, Cl green, O red, C white, Mg orange) exhibited compatibility with magnesium-metal anodes as well as remarkable oxidative stability (3.2 V vs. Mg) on non-noble-metal electrodes.

    18. Kinetic Resolution

      Ruthenium-Catalyzed Oxidative Kinetic Resolution of Unactivated and Activated Secondary Alcohols with Air as the Hydrogen Acceptor at Room Temperature (pages 3178–3182)

      Hirotaka Mizoguchi, Dr. Tatsuya Uchida and Prof. Tsutomu Katsuki

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201310426

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      Alcohol resolution: An (aqua)ruthenium salen complex catalyzes the efficient oxidative kinetic resolution of both activated and unactivated secondary alcohols with air as the hydrogen acceptor at room temperature. The reaction is compatible with various functional groups, including halogen, ether, silyl ether, and ester groups. The reaction rate is lower at higher substrate concentrations as a result of substrate inhibition.

    19. Cross-Coupling

      Aryl Formate as Bifunctional Reagent: Applications in Palladium-Catalyzed Carbonylative Coupling Reactions Using In Situ Generated CO (pages 3183–3186)

      Haoquan Li, Dr. Helfried Neumann, Prof. Dr. Matthias Beller and Dr. Xiao-Feng Wu

      Version of Record online: 14 FEB 2014 | DOI: 10.1002/anie.201311198

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      Transformers: A versatile and practical protocol for carbonylation reactions involve the cooperation of phenyl formate and nonaflate with generation of CO in situ. This protocol has a high functional-group tolerance and could be applied in carbonylative couplings with C, N, and O nucleophiles. The corresponding amides, alkynones, furanones, and aryl benzoates were synthesized in good yield.

    20. Carbocycles

      A New Type of Donor–Acceptor Cyclopropane Reactivity: The Generation of Formal 1,2- and 1,4-Dipoles (pages 3187–3191)

      Roman A. Novikov, Anna V. Tarasova, Victor A. Korolev, Vladimir P. Timofeev and Yury V. Tomilov

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/anie.201306186

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      Old ring, new reactivity: A new type of donor–acceptor cyclopropane reactivity has been discovered. On treatment with anhydrous GaCl3, they react as sources of even-numbered 1,2- and 1,4-dipoles instead of the classical odd-numbered 1,3-dipoles owing to the migration of positive charge from the benzyl center.

    21. Lipid Membranes

      Monitoring and Quantifying the Passive Transport of Molecules Through Patch–Clamp Suspended Real and Model Cell Membranes (pages 3192–3196)

      Dr. Pierluca Messina, Dr. Frédéric Lemaître, Prof. François Huet, Dr. Kieu An Ngo, Dr. Vincent Vivier, Prof. Eric Labbé, Dr. Olivier Buriez and Prof. Christian Amatore

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201308990

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      More than patched up: Electrochemical detection of molecular species crossing suspended membranes is possible by a novel integration of patch–clamp and amperometry. This approach provides a powerful means for quantifying, in real time, fluxes of molecular species across real cell and artificial membranes.

    22. Aminocyanation

      Formal Aminocyanation of α,β-Unsaturated Cyclic Enones for the Efficient Synthesis of α-Amino Ketones (pages 3197–3200)

      Chunrui Sun, Matthew J. O'Connor, Prof. Daesung Lee, Prof. Donald J. Wink and Robert D. Milligan

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201309435

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      Make and break: 1,2-Aminocyanation was achieved through a formal dipolar cycloaddition of cyclic α,β-unsaturated ketones with lithium trimethylsilyldiazomethane to generate pyrazoline followed by protonolytic N[BOND]N bond cleavage. This reaction provides an efficient method for the synthesis of a diverse array of structurally complex and novel α-amino ketones.

    23. Nanomotors

      Acoustic Propulsion of Nanorod Motors Inside Living Cells (pages 3201–3204)

      Prof. Wei Wang, Sixing Li, Dr. Lamar Mair, Suzanne Ahmed, Prof. Tony Jun Huang and Prof. Thomas E. Mallouk

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201309629

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      Ultrasonic propulsion: Metallic nanomotors can be internalized by incubation with HeLa cells for periods longer than 24 h (see picture). Once inside the cells, the nanomotors can be activated by resonant ultrasound operating at 4 MHz, and show axial propulsion as well as spinning. The HeLa cells remain viable.

    24. Catalytic Materials

      Tunable Oxygen Activation for Catalytic Organic Oxidation: Schottky Junction versus Plasmonic Effects (pages 3205–3209)

      Ran Long, Keke Mao, Ming Gong, Shan Zhou, Jiahua Hu, Min Zhi, Yang You, Song Bai, Prof. Jun Jiang, Prof. Qun Zhang, Prof. Xiaojun Wu and Prof. Yujie Xiong

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201309660

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      All things in moderation: The charge state of the Pd surface is critical to the ability of Pd nanocrystals to promote oxygen activation (see picture). Thus, the catalytic efficiency of Pd nanocrystals in organic oxidation reactions can be tuned by simply varying the intensity of light shed on palladium–semiconductor hybrid structures. Under strong illumination, a plasmonic effect may cause the reverse migration of electrons from Pd to TiO2.

    25. Weak Hydrogen Bonds

      Probing the C[BOND]H⋅⋅⋅π Weak Hydrogen Bond in Anesthetic Binding: The Sevoflurane–Benzene Cluster (pages 3210–3213)

      Nathan A. Seifert, Dr. Daniel P. Zaleski, Dr. Cristóbal Pérez, Dr. Justin L. Neill, Prof. Brooks H. Pate, Montserrat Vallejo-López, Prof. Alberto Lesarri, Dr. Emilio J. Cocinero, Prof. Fernando Castaño and Prof. Isabelle Kleiner

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201309848

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      Cooperation is force: The cooperativity between a primary C[BOND]H⋅⋅⋅π hydrogen bond and multiple C[BOND]H⋅⋅⋅F weak interactions defines the dynamic nonbonding union between sevoflurane and benzene. The structure and internal rotation was determined with broadband rotational spectroscopy.

    26. Synthetic Methods

      Metal Alkoxide Promoted Regio- and Stereoselective C[DOUBLE BOND]O and C[DOUBLE BOND]C Metathesis of Allenoates with Aldehydes (pages 3214–3217)

      Minyan Wang, Dr. Zhao Fang, Prof. Dr. Chunling Fu and Prof. Dr. Shengming Ma

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/anie.201310183

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      All'ene' all: The reaction of aldehydes with 2,3-allenoates in the presence of tBuOM (M=Li or Na) affords the stereodefined, highly functionalized γ,δ-unsaturated β-ketoesters 1 in good to excellent yields with E stereoselectivity. The reactivity of 5-hydroxy-2,3-allenoates and the isolation of 3,4-diaryloxetanes led to a rationale for the mechanism of the reaction.

    27. Quasi-Stable Pincer Ligands

      On the Stability of a POCsp3OP-Type Pincer Ligand in Nickel(II) Complexes (pages 3218–3222)

      Dr. Jingjun Hao, Berline Mougang-Soumé, Boris Vabre and Prof. Dr. Davit Zargarian

      Version of Record online: 14 FEB 2014 | DOI: 10.1002/anie.201310386

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      Survival of the fittest: One or both of the C[BOND]O linkages in the complex [(POCsp3OP)Ni(OSiMe3)] break under fairly mild conditions to generate unprecedented mono- and trinuclear species. These decomposition processes can serve as models for predicting the stabilities of these complexes in catalytic settings.

    28. Amination

      Room-Temperature Amination of Deactivated Aniline and Aryl Halide Partners with Carbonate Base Using a Pd-PEPPSI-IPentCl- o-Picoline Catalyst (pages 3223–3226)

      Matthew Pompeo, Jennifer L. Farmer, Dr. Robert D. J. Froese and Prof. Michael G. Organ

      Version of Record online: 14 FEB 2014 | DOI: 10.1002/anie.201310457

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      Running mild: An N-heterocyclic carbene complex of palladium (1) was systematically designed to enable the amination of strongly deactivated substrates (R1 can be strongly electron donating, R2 can be strongly electron-withdrawing) when using the most mild of bases (carbonate) at room temperature. This catalyst was used to produce elaborate, richly functionalized products for use in life-, health-, and material-science applications.

    29. Synthetic Methods

      Double Transfer of Chirality in Organocopper-Mediated bis(Alkylating) Cycloisomerization of Enediynes (pages 3227–3231)

      Dr. Damien Campolo, Dr. Tanzeel Arif, Cyril Borie, Dr. Dominique Mouysset, Dr. Nicolas Vanthuyne, Dr. Jean-Valère Naubron, Prof. Michèle P. Bertrand and Dr. Malek Nechab

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/anie.201310530

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      Double duty: An original synthesis of chiral benzofulvenes was developed through the highly chemo-, regio-, diastereo-, and enantioselective double transfer of alkyl groups to electrophilic enediynes. This organocopper-triggered cycloisomerization proceeds with double transfer of chirality (central-to-axial-to-central).

    30. C[BOND]C Coupling

      Redox-Triggered C[BOND]C Coupling of Diols and Alkynes: Synthesis of β,γ-Unsaturated α-Hydroxyketones and Furans by Ruthenium-Catalyzed Hydrohydroxyalkylation (pages 3232–3235)

      Emma L. McInturff, Khoa D. Nguyen and Prof. Michael J. Krische

      Version of Record online: 14 FEB 2014 | DOI: 10.1002/anie.201311130

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      More alcohol, more fun: Diols and alkynes engage in ruthenium(0)-catalyzed hydrohydroxyalkylation to form β,γ-unsaturated ketones with good to complete levels of regioselectivity and control of alkene geometry. Exposure of the reaction products to p-toluenesulfonic acid results in cyclodehydration to form tetrasubstituted furans.

    31. Chemoselectivity

      Highly Chemoselective Aerobic Oxidation of Amino Alcohols into Amino Carbonyl Compounds (pages 3236–3240)

      Yusuke Sasano, Shota Nagasawa, Mai Yamazaki, Dr. Masatoshi Shibuya, Prof. Dr. Jaiwook Park and Prof. Dr. Yoshiharu Iwabuchi

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/anie.201309634

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      Strong as an ox: The highly chemoselective aerobic oxidation of unprotected amino alcohols to their corresponding amino carbonyl compounds has been achieved by using 2-azaadamantane N-oxyl (AZADO)/copper catalysis. This catalytic system oxidizes not only alcohols with tertiary amino groups but also those with secondary and primary amines in good to high yield at ambient temperature in air. bpy=2,2-bipyridyl, DMAP=4-(N,N-dimethylamino)pyridine.

    32. Hydroboration

      Direct Hydroboration of B[DOUBLE BOND]B Bonds: A Mild Strategy for the Proliferation of B[BOND]B Bonds (pages 3241–3244)

      Prof. Dr. Holger Braunschweig, Dr. Rian D. Dewhurst, Dipl.-Chem. Christian Hörl, Dr. Ashwini K. Phukan, Florian Pinzner and Stefan Ullrich

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/anie.201309325

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      H. C. Brown meets diborenes: The few existing strategies for the construction of electron-precise boron chains involve either strongly reducing reagents or transition-metal catalysts; both have distinct disadvantages. Thus, the direct hydroboration of diborenes to form new B[BOND]B bonds and B3 chains is presented. The reaction is diastereoselective and proceeds under mild conditions without the use of strong reducing agents or transition-metal catalysts. IMe=1,3-dimethylimidazol-2-ylidene; E=O, S.

    33. Heterogeneous Catalysis

      Low-Temperature Oxidation of Carbon Monoxide with Gold(III) Ions Supported on Titanium Oxide (pages 3245–3249)

      Prof. Wolfgang Grünert, Dr. Dennis Großmann, Dr. Heshmat Noei, Dr. Marga-Martina Pohl, Dr. Ilya Sinev, Dr. Andrea De Toni, Dr. Yuemin Wang and Prof. Martin Muhler

      Version of Record online: 19 FEB 2014 | DOI: 10.1002/anie.201308206

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      Ionic or metallic: Au3+ ions on TiO2 (see HAADF-STEM image of a freshly prepared sample) can catalyze the oxidation of CO at low temperatures. The reaction rates at Au3+-containing centers are similar to those found at metallic gold clusters. However, the apparent activation energies are very low, which is probably due to the opposing influence of the true activation energy and the adsorption enthalpy of CO on Au3+ centers.

    34. Diazenium Ions

      Isolation of a Labile Homoleptic Diazenium Cation (pages 3250–3253)

      Dr. Wolfgang Baumann, Dr. Dirk Michalik, Fabian Reiß, Prof. Dr. Axel Schulz and Dr. Alexander Villinger

      Version of Record online: 14 FEB 2014 | DOI: 10.1002/anie.201310186

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      Cold, blue, and positive: The first homoleptic diazenium cation has been formed by treating mercury(II) dihydrazide with Ag[GaCl4] at low temperature. While numerous attempts at the direct silylation of diazene failed, this alternative new two-electron oxidation of the trisilylated hydrazide ion affords blue, highly labile [(Me3Si)2N[DOUBLE BOND]N-SiMe3]+ ions in almost quantitative yield.

    35. Topochemistry

      The Topochemical Pseudomorphosis of a Chloride into a Bismuthide (pages 3254–3258)

      Martin Kaiser, Bertold Rasche and Prof. Dr. Michael Ruck

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201309460

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      Breathe in: In the dense structure of Bi12Rh3Cl2, chloride ions are replaced by bismuth atoms in the course of a heterogeneous topochemical reaction. The vast mass transport through the crystal at only 70 °C is enabled by a breathing mode of the intermetallic framework, which opens diffusion paths by varying the inclination ω (see picture). The complete exchange yields the metastable superconductor Bi12Rh3Bi2.

    36. Enzyme Inhibitors

      Structure-Based Design of Inhibitors of the Aspartic Protease Endothiapepsin by Exploiting Dynamic Combinatorial Chemistry (pages 3259–3263)

      Milon Mondal, Nedyalka Radeva, Dr. Helene Köster, Dr. Ahyoung Park, Dr. Constantinos Potamitis, Dr. Maria Zervou, Prof. Dr. Gerhard Klebe and Dr. Anna K. H. Hirsch

      Version of Record online: 14 FEB 2014 | DOI: 10.1002/anie.201309682

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      The dynamic duo: The combination of de novo structure-based design and dynamic combinatorial chemistry has been applied to the identification of novel acylhydrazone-based inhibitors for the aspartic protease endothiapepsin. 1H-STD-NMR spectroscopy has been used to identify the binders from the dynamic combinatorial libraries. Proposed binding modes of the most potent inhibitors have been confirmed by X-ray crystallography.

    37. Photopharmacology

      A Photochromic Agonist for μ-Opioid Receptors (pages 3264–3267)

      Matthias Schönberger and Prof. Dr. Dirk Trauner

      Version of Record online: 12 FEB 2014 | DOI: 10.1002/anie.201309633

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      Lighting up the opioid receptor: Photofentanyl-2 is a photochromic version of the well-known analgesic fentanyl. It is a potent agonist in the dark (or when illuminated with blue light) and loses activity when irradiated with UV light. It can be used to optically control the μ-opioid receptor, converting a G-protein-coupled receptor (GPCR) into a photoreceptor.

  12. And Finally

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Author Profile
    7. News
    8. Obituary
    9. Book Reviews
    10. Highlights
    11. Review
    12. Communications
    13. And Finally
    1. Carl Djerassi

      Carl Djerassi: In His Own Words (pages 3268–3279)

      Dr. Jeffrey I. Seeman

      Version of Record online: 11 MAR 2014 | DOI: 10.1002/anie.201308367

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      In honor of the 90th birthday of Professor Carl Djerassi, J. I. Seeman has assembled a collection of poignant quotes and excerpts from Djerassi's writings which embody his remarkable life experiences, his philosophies of life, and his unique personality.

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