Angewandte Chemie International Edition

Cover image for Angewandte Chemie International Edition

October 1, 2012

Volume 51, Issue 40

Pages 9943–10193

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. You have free access to this content
      Cover Picture: Epidithiol Formation by an Unprecedented Twin Carbon–Sulfur Lyase in the Gliotoxin Pathway (Angew. Chem. Int. Ed. 40/2012) (page 9943)

      Daniel H. Scharf, Pranatchareeya Chankhamjon, Dr. Kirstin Scherlach, Dr. Thorsten Heinekamp, Dr. Martin Roth, Prof. Dr. Axel A. Brakhage and Prof. Dr. Christian Hertweck

      Version of Record online: 13 SEP 2012 | DOI: 10.1002/anie.201206982

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      The pathogenic fungus Aspergillus fumigatus produces the infamous toxin, gliotoxin. In their Communication on page 10064 ff., C. Hertweck and co-workers elucidate a key step in the biosynthesis of the transannular disulfide bridge that is indispensable for the deleterious effects of gliotoxin. A single enzyme, GliI, is capable of concomitantly cleaving two C[BOND]S bonds in a bis(cysteinyl) adduct, to yield a dithiol, ammonia, and pyruvate. Electron micrograph kindly provided by J. Schmaler-Ripcke, Jena.

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      Inside Cover: Hysteretic Three-Step Spin Crossover in a Thermo- and Photochromic 3D Pillared Hofmann-type Metal–Organic Framework (Angew. Chem. Int. Ed. 40/2012) (page 9944)

      Dr. Natasha F. Sciortino, Dr. Katrin R. Scherl-Gruenwald, Dr. Guillaume Chastanet, Dr. Gregory J. Halder, Dr. Karena W. Chapman, Prof. Jean-François Létard and Prof. Cameron J. Kepert

      Version of Record online: 23 SEP 2012 | DOI: 10.1002/anie.201207301

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      Multistable molecular materials address fundamental questions in the solid state and promise application in a range of molecular devices. In their Communication on page 10154 ff. C. J. Kepert and co-workers present a metal–organic framework that exhibits a unique hysteretic three-step spin-crossover transition. The transition spans four separate lattice spin states and includes two temperature regions over which the material is formally tristable; that is, three of the four states are stable within each of these regions and may be individually accessed through thermal control. (Graphic design by Karl Mutimer.)

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      Inside Back Cover: Can Hindered Intramolecular Vibrational Energy Redistribution Lead to Non-Ergodic Behavior of Medium-Sized Ion Pairs? (Angew. Chem. Int. Ed. 40/2012) (page 10195)

      Dr. Christopher J. Shaffer, Dr. Ágnes Révész, Dr. Detlef Schröder, Ing. Lukáš Severa, Dr. Filip Teplý, Dr. Emilie-Laure Zins, Mgr. Lucie Jašíková and Dr. Jana Roithová

      Version of Record online: 26 SEP 2012 | DOI: 10.1002/anie.201207222

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      Too much heat in non-covalent complexes leads to non-ergodic behavior in ion pairs of nitrogen-containing cations with triflate counterions. In their Communication on page 10050 ff., D. Schröder et al. show by means of infrared spectroscopy of mass-selected ions that the effect is caused by incomplete intramolecular vibrational energy distribution, leading to a local “overheating” of the triflate counterions. PS: Find the hidden dedication in the picture! The puzzle will be solved on the homepage of ChemViews Magazine (http://www.chemviews.org).

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      Back Cover: The Impact of Ligand Reorganization on Cerium(III) Oxidation Chemistry (Angew. Chem. Int. Ed. 40/2012) (page 10196)

      Jerome R. Robinson, Dr. Patrick J. Carroll, Prof. Patrick J. Walsh and Prof. Eric J. Schelter

      Version of Record online: 13 SEP 2012 | DOI: 10.1002/anie.201206981

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      The control of ligand reorganization is a new design strategy for cerium(III) redox chemistry, and allows for the prediction of reaction products. In their Communication on page 10159 ff., P. J. Walsh, E. J. Schelter, and co-workers report alkali-metal/cerium heterobimetallic complexes that modulate ligand reorganization. The picture shows electron transfer between two complexes near the planetoid Ceres, under the watchful gaze of the eponymous goddess.

  2. Graphical Abstract

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. You have free access to this content
      Corrigendum: Solid-State NMR Measurements of Asymmetric Dipolar Couplings Provide Insight into Protein Side-Chain Motion (page 9959)

      Dr. Paul Schanda, Matthias Huber, Dr. Jérôme Boisbouvier, Prof. Dr. Beat H. Meier and Prof. Dr. Matthias Ernst

      Version of Record online: 26 SEP 2012 | DOI: 10.1002/anie.201206663

      This article corrects:
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  4. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. Atsuhiro Osuka (pages 9970–9971)

      Version of Record online: 25 MAY 2012 | DOI: 10.1002/anie.201203104

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      “If I were not a scientist, I would be a painter. The most significant scientific advance of the last 100 years has been the Haber–Bosch process for ammonia synthesis …” This and more about Atsuhiro Osuka can be found on page 9970.

  6. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. Radical Enzymes

      Hydrogen Bonds Guide the Short-Lived 5′-Deoxyadenosyl Radical to the Place of Action (pages 9974–9976)

      Prof. Dr. Wolfgang Buckel, Dr. Peter Friedrich and Prof. Dr. Bernard T. Golding

      Version of Record online: 3 SEP 2012 | DOI: 10.1002/anie.201205299

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      Radical chaperone: Recent research reveals how the 5′-deoxyadenosyl radical (see structure) is generated by homolysis of the Co[BOND]C σ-bond of enzyme-bound coenzyme B12 and how it is guided to the substrate through pseudorotation of the ribose moiety and hydrogen-bonding interactions.

    2. Boron Materials

      Enforced Planarity: A Strategy for Stable Boron-Containing π-Conjugated Materials (pages 9977–9979)

      Juan F. Araneda, Dr. Benedikt Neue and Prof. Warren E. Piers

      Version of Record online: 29 AUG 2012 | DOI: 10.1002/anie.201205265

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      Catching a plane: A new strategy for stabilizing the B[BOND]C bonds in boron-containing π-conjugated materials has been demonstrated. Encasing the boron in a rigid, planarized environment (see scheme) has been shown by Yamaguchi and co-workers to give air- and moisture-stable organoboranes that bring the boron's p orbital into full conjugation with the organic π framework.

  8. Minireview

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. Asymmetric Catalysis

      Silyl Ketene Imines: Highly Versatile Nucleophiles for Catalytic, Asymmetric Synthesis (pages 9980–9992)

      Prof. Dr. Scott E. Denmark and Dr. Tyler W. Wilson

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/anie.201202139

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      Teaching a middled-aged nucleophile new tricks: This Minireview provides an overview on the development of silyl ketene imines and their recent applications in catalytic, enantioselective reactions. The unique structure of ketene imines allow a diverse range of reactivity patterns and provide solutions to existing challenges in the enantioselective construction of quaternary stereogenic carbon centers and cross-benzoin adducts (see scheme; Pg=protecting group, Y=OPg).

  9. Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. Batteries

      Challenges Facing Lithium Batteries and Electrical Double-Layer Capacitors (pages 9994–10024)

      Prof. Nam-Soon Choi, Dr. Zonghai Chen, Dr. Stefan A. Freunberger, Dr. Xiulei Ji, Prof. Yang-Kook Sun, Prof. Khalil Amine, Prof. Gleb Yushin, Prof. Linda F. Nazar, Prof. Jaephil Cho and Prof. Peter G. Bruce

      Version of Record online: 10 SEP 2012 | DOI: 10.1002/anie.201201429

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      TrueLi advanced: Modern energy storage technologies, such as lithium batteries and electrical double-layer capacitors are a central area of basic research. The aims being to develop new materials and electrochemical reactions for these energy storage units and to better understand the underlying processes. Latest developments include the Li–air (see picture) and the Li–S batteries

  10. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Highlights
    9. Minireview
    10. Review
    11. Communications
    1. Electron Transfer

      Photoinduced Reductive Electron Transfer in LNA:DNA Hybrids: A Compromise between Conformation and Base Stacking (pages 10026–10029)

      Dipl.-Chem. Ulrike Wenge, Prof. Jesper Wengel and Prof. Hans-Achim Wagenknecht

      Version of Record online: 3 SEP 2012 | DOI: 10.1002/anie.201204901

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      Lock it, but not too much: LNA units (locked or bridging nucleic acids) in LNA:DNA hybrids lead to a negative effect on electron transfer (ET), but they also force the nucleic acid structure in the A-type double helix, which allows a better base stacking than the normal B-type and thus positively influences the ET. This result is significant for the design of nucleic acids of molecular electronics.

    2. Heterobimetallic Complexes

      Reversible Insertion of Platinum into Coinage Group Metal–Halogen Bonds (pages 10030–10033)

      Jürgen Bauer, Prof. Dr. Holger Braunschweig, Alexander Damme and Dr. Krzysztof Radacki

      Version of Record online: 7 SEP 2012 | DOI: 10.1002/anie.201205438

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      M&Ms: The reversible insertion of a platinum complex into coinage group metal–halogen bonds results in a series of unsupported metal-only Lewis pairs with a Lewis basic platinum(0) fragment and cationic copper, silver, and gold Lewis acids (see scheme; M=Cu, Ag, Au; Cy=cyclohexyl). This is a convenient route to mixed d10–d10 complexes.

    3. Boron Heterocycles

      Metal-Mediated Synthesis of 1,4-Di-tert-butyl-1,4-azaborine (pages 10034–10037)

      Prof. Dr. Holger Braunschweig, Alexander Damme, Dr. J. Oscar C. Jimenez-Halla, Bernd Pfaffinger, Dr. Krzysztof Radacki and Dr. Justin Wolf

      Version of Record online: 5 SEP 2012 | DOI: 10.1002/anie.201205795

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      Completing the set: Although 1,2-azaborine is known, little is known about the 1,3- and 1,4-analogues. Now a simple, controlled synthesis of 1,2-di-tert-butyl-1,2-azaborine from acetylene and di-tert-butyliminoborane has been achieved by a metal-mediated formal [2+2+2] cycloaddition reaction. A 1,2-azaborete pianostool complex was identified as an reaction intermediate.

    4. Energetic Materials

      2,4,6-Trinitrotoluene: A Surprisingly Insensitive Energetic Fuel and Binder in Melt-Cast Decoy Flare Compositions (pages 10038–10040)

      Dr. Ernst-Christian Koch, Volker Weiser and Evelin Roth

      Version of Record online: 7 SEP 2012 | DOI: 10.1002/anie.201204808

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      Deceiving with TNT: Melt-cast pyrotechnic mixtures based on 2,4,6-trinitrotoluene (TNT)/KClO4 (see picture for flame) spectrally matched infrared decoy flares and show superior performance and greatly reduced sensitivity in comparison to common pyrotechnic or double-base material currently in use for IR countermeasure flares.

    5. Heterogeneous Catalysis

      You have full text access to this OnlineOpen article
      Local Catalytic Ignition during CO Oxidation on Low-Index Pt and Pd Surfaces: A Combined PEEM, MS, and DFT Study (pages 10041–10044)

      Diana Vogel, Dr. Christian Spiel, Prof. Dr. Yuri Suchorski, Adriana Trinchero, Prof. Dr. Robert Schlögl, Prof. Dr. Henrik Grönbeck and Prof. Dr. Günther Rupprechter

      Version of Record online: 7 SEP 2012 | DOI: 10.1002/anie.201204031

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      Shedding light on light-off: Photoemission electron microscopy, DFT, and microkinetic modeling were used to examine the local kinetics in the CO oxidation on individual grains of a polycrystalline sample. It is demonstrated that catalytic ignition (“light-off”) occurs easier on Pd(hkl) domains than on corresponding Pt(hkl) domains. The isothermal determination of kinetic transitions, commonly used in surface science, is fully consistent with the isobaric reactivity monitoring applied in technical catalysis.

    6. Molecular Nanoswitches

      The Carboxylate Twist: Hysteretic Bistability of a High-Spin Diiron(II) Complex Identified by Mössbauer Spectroscopy (pages 10045–10049)

      Boris Burger, Dr. Serhiy Demeshko, Dr. Eckhard Bill, Dr. Sebastian Dechert and Prof. Dr. Franc Meyer

      Version of Record online: 10 SEP 2012 | DOI: 10.1002/anie.201202759

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      In a twist: The carboxylate ligand in the clamp of a highly preorganized diferrous site shows temperature-dependent dynamic behavior, coined the “carboxylate twist”. It leads to a fluctuation of the electric field gradient and thus averaged Mössbauer resonances at higher temperatures, resulting in magnetic and spectroscopic hysteresis even without any spin-crossover or valence tautomerism.

    7. Ion Pairs

      Can Hindered Intramolecular Vibrational Energy Redistribution Lead to Non-Ergodic Behavior of Medium-Sized Ion Pairs? (pages 10050–10053)

      Dr. Christopher J. Shaffer, Dr. Ágnes Révész, Dr. Detlef Schröder, Ing. Lukáš Severa, Dr. Filip Teplý, Dr. Emilie-Laure Zins, Mgr. Lucie Jašíková and Dr. Jana Roithová

      Version of Record online: 15 AUG 2012 | DOI: 10.1002/anie.201203441

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      Communication breakdown: Ergodicity is the ability to predict the behavior of an ensemble from the behavior of its components. Infrared spectroscopy of mass-selected ion pairs in the gas phase suggests that intramolecular vibrational energy redistribution (IVR) is hindered in some of these noncovalently bound species, particularly when triflate anion is involved. The hindered IVR leads to a non-ergodic behavior on a timescale sufficient for the formation of new chemical bonds.

    8. Drug Design

      You have full text access to this OnlineOpen article
      Development of a Peptide that Selectively Activates Protein Phosphatase-1 in Living Cells (pages 10054–10059)

      Dr. Jayanta Chatterjee, Prof. Monique Beullens, Dr. Rasa Sukackaite, Junbin Qian, Dr. Bart Lesage, Dr. Darren J. Hart, Prof. Mathieu Bollen and Dr. Maja Köhn

      Version of Record online: 7 SEP 2012 | DOI: 10.1002/anie.201204308

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      The first cell-penetrating peptide that activates protein phosphatase-1 (PP1) by disrupting a subset of PP1 complexes in living cells has been developed. Activated PP1 rapidly dephosphorylates its substrates, counteracting kinase activity inside cells. Activation of PP1 can thus be a novel approach to study PP1 function and to counteract Ser/Thr kinase activity under pathologically increased kinase signaling.

    9. Artificial Membranes

      Dynamic Interface Imprinting: High-Affinity Peptide Binding Sites Assembled by Analyte-Induced Recruiting of Membrane Receptors (pages 10060–10063)

      Dipl.-Chem. Benjamin Gruber, M. Sc. Stefan Balk, Dr. Stefan Stadlbauer and Prof. Dr. Burkhard König

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/anie.201205701

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      Come together: Dynamic molecular recognition events at biological membrane receptors play a key role in cell signaling. Artificial membranes have been prepared with embedded synthetic receptors which dynamically arrange and selectively respond to external stimuli, such as, small peptide ligands.

    10. Natural Sulfur Compounds

      Epidithiol Formation by an Unprecedented Twin Carbon–Sulfur Lyase in the Gliotoxin Pathway (pages 10064–10068)

      Daniel H. Scharf, Pranatchareeya Chankhamjon, Dr. Kirstin Scherlach, Dr. Thorsten Heinekamp, Dr. Martin Roth, Prof. Dr. Axel A. Brakhage and Prof. Dr. Christian Hertweck

      Version of Record online: 31 AUG 2012 | DOI: 10.1002/anie.201205041

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      Two in one go: The elucidation of a key step in the biosynthesis of gliotoxin, the infamous virulence factor of the human pathogen Aspergillus fumigatus, provides insight into the formation of an epidithiol. Isolation of a bis(cysteine) S-conjugate from a ΔgliI mutant and in vitro studies show that GliI concomitantly cleaves two C[BOND]S bonds, along with the formation of ammonia and pyruvate (see scheme).

    11. Asymmetric Synthesis

      Highly Enantio- and Diastereoselective Reactions of γ-Substituted Butenolides Through Direct Vinylogous Conjugate Additions (pages 10069–10073)

      Wen Zhang, Davin Tan, Richmond Lee, Guanghu Tong, Wenchao Chen, Baojian Qi, Prof. Dr. Kuo-Wei Huang, Prof. Dr. Choon-Hong Tan and Prof. Dr. Zhiyong Jiang

      Version of Record online: 5 SEP 2012 | DOI: 10.1002/anie.201205872

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      The strength of the weak: An L-tert-leucine-derived amine–thiourea catalyst (see scheme, green box) promotes the asymmetric vinylogous conjugate addition reaction between γ-aryl- and alkyl-substituted butenolides with the butenamides and enoates shown. Computational studies show the preference for the observed stereochemistry is a result of favourable weak non-bonding interactions, which stabilize the transition state.

    12. Silicon Chemistry

      The Elusive Silyliumylidene [ClSi:]+ and Silathionium [ClSi[DOUBLE BOND]S]+ Cations Stabilized by Bis(Iminophosphorane) Chelate Ligand (pages 10074–10077)

      Dr. Yun Xiong, Dr. Shenglai Yao, Prof. Dr. Shigeyoshi Inoue, Dr. Elisabeth Irran and Prof. Dr. Matthias Driess

      Version of Record online: 10 SEP 2012 | DOI: 10.1002/anie.201205840

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      Donor–acceptor trumps: The chlorosilyliumylidene salt 2 with a three-coordinate silicon(II) atom is accessible through ligand exchange between NHC[BOND]SiCl2 and the electron-rich bis(ylide) ligand 1. The cation in 2 represents a donor-stabilized form of the elusive [ClSi:] cation and could be fully characterized, including X-ray diffraction analysis. Oxidation of 2 with elemental sulfur furnished 3 as the sole product.

    13. Ligand Design

      You have full text access to this OnlineOpen article
      Using Ligand-Mapping Simulations to Design a Ligand Selectively Targeting a Cryptic Surface Pocket of Polo-Like Kinase 1 (pages 10078–10081)

      Yaw Sing Tan, Dr. Paweł Śledź, Dr. Steffen Lang, Christopher J. Stubbs, Dr. David R. Spring, Prof. Chris Abell and Dr. Robert B. Best

      Version of Record online: 7 SEP 2012 | DOI: 10.1002/anie.201205676

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      An explicit solvent ligand-mapping approach was used to reveal an otherwise hidden hydrophobic pocket in polo-like kinase 1 (Plk1). It predicted a novel ligand binding mode that was used for the design of a new ligand with high affinity for Plk1. X-ray crystallography confirmed that the binding was specific to the intended pocket.

    14. Crystal Engineering

      Crystal Engineering of a Microporous, Catalytically Active fcu Topology MOF Using a Custom-Designed Metalloporphyrin Linker (pages 10082–10085)

      Le Meng, Qigan Cheng, Chungsik Kim, Wen-Yang Gao, Lukasz Wojtas, Yu-Sheng Chen, Prof. Michael J. Zaworotko, Prof. X. Peter Zhang and Prof. Shengqian Ma

      Version of Record online: 5 SEP 2012 | DOI: 10.1002/anie.201205603

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      A 12-connected fcu metal–organic framework (MOF), MMPF-3, has been prepared using a CoII metalloporphyrin. MMPF-3 is comprised of the same polyhedral supermolecular building blocks as the prototypal fcu-MOF, fcu-MOF-1, and its nanoscale cavities feature 18 catalytically active cobalt centers. The high density (ca. 5 cobalt sites/nm3) affords MMPF-3 superior performance in catalytic epoxidation of trans-stilbene compared to other MOFs.

    15. Benzene Hexafluoride

      The Synthesis of η-1,2,3,4,5,6-Hexafluorocyclohexane (Benzene Hexafluoride) from Benzene (pages 10086–10088)

      Alastair J. Durie, Prof. Alexandra M. Z. Slawin, Dr. Tomas Lebl and Prof. David O'Hagan

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/anie.201205577

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      Six of the best: Benzene had been used by Faraday and Mitscherlich in their respective synthesis of hexachloro- and hexabromocyclohexane in the early 19th century. Also starting from benzene, η-1,2,3,4,5,6-hexafluorocyclohexane (benzene hexafluoride; see X-ray structure of a dimer) was now synthesized in five steps.

    16. Anticancer Agents

      A Liposomal System Capable of Generating CO2 Bubbles to Induce Transient Cavitation, Lysosomal Rupturing, and Cell Necrosis (pages 10089–10093)

      Min-Fan Chung, Ko-Jie Chen, Hsiang-Fa Liang, Zi-Xian Liao, Wei-Tso Chia, Prof. Younan Xia and Prof. Hsing-Wen Sung

      Version of Record online: 5 SEP 2012 | DOI: 10.1002/anie.201205482

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      Bubbling over: After endocytosis and intracellular trafficking to lysosomes, liposomes containing ammonium bicarbonate can be thermally triggered to generate CO2 bubbles (see scheme). These bubbles grow rapidly and collapse violently to induce transient cavitation, a process that can disrupt the lysosomal membrane and release lysosomal proteases, thus leading to cell necrosis.

    17. Template Synthesis

      Using Host–Guest Complexation to Fold a Flexible Linear Organic String: Kinetically Controlled Syntheses of [3]Catenanes and a Five-Membered Molecular Necklace (pages 10094–10098)

      Chia-Fong Chang, Chun-Ju Chuang, Prof. Chien-Chen Lai, Yi-Hung Liu, Prof. Shie-Ming Peng and Prof. Sheng-Hsien Chiu

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/anie.201205498

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      Rings and necklaces: Three [3]catenanes and a five-membered molecular necklace ([5]MN), with up to 60- and 92-membered rings as their centerpieces, respectively, have been synthesized. The synthesis started from the corresponding complexes in which the threaded flexible linear guests were bent at approximately right angles to facilitate kinetically controlled macrocyclizations.

    18. Metal–Organic Frameworks

      On Demand: The Singular rht Net, an Ideal Blueprint for the Construction of a Metal–Organic Framework (MOF) Platform (pages 10099–10103)

      Dr. Jarrod F. Eubank, Dr. Farid Nouar, Ryan Luebke, Dr. Amy J. Cairns, Dr. Lukasz Wojtas, Dr. Mohamed Alkordi, Dr. Till Bousquet, Matthew R. Hight, Dr. Juergen Eckert, Dr. Jan P. Embs, Dr. Peter A. Georgiev and Prof. Dr. Mohamed Eddaoudi

      Version of Record online: 7 SEP 2012 | DOI: 10.1002/anie.201201202

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      The exceptional nature of the rht-MOF platform, based on a singular edge-transitive net (the only net for the combination of 3- and 24-connected nodes), makes it an ideal target in crystal chemistry. The high level of control indicates an unparalleled blueprint for isoreticular functional materials (without concern for interpenetration) for targeted applications.

    19. Excited-State Tuning

      Controllably Tuning Excited-State Energy in Ternary Hosts for Ultralow-Voltage-Driven Blue Electrophosphorescence (pages 10104–10108)

      Chunmiao Han, Zhensong Zhang, Dr. Hui Xu, Jing Li, Dr. Guohua Xie, Dr. Runfeng Chen, Prof. Yi Zhao and Prof. Wei Huang

      Version of Record online: 7 SEP 2012 | DOI: 10.1002/anie.201202702

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      A series of dibenzofuran-based ternary hosts were designed and prepared. The singlet energy levels and carrier injecting/transporting abilities were adjusted on the basis of the mixed meso and short-axis linkages (see picture). By harmonizing the optical and electrical properties, the blue-emitting diodes realized highly efficient blue electrophosphorescence with ultralow driving voltages.

    20. Smart Materials

      Patterned Superomniphobic–Superomniphilic Surfaces: Templates for Site-Selective Self-Assembly (pages 10109–10113)

      Sai P. R. Kobaku, Dr. Arun K. Kota, Dr. Duck Hyun Lee, Dr. Joseph M. Mabry and Prof. Anish Tuteja

      Version of Record online: 31 AUG 2012 | DOI: 10.1002/anie.201202823

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      Patterned surfaces: The fabrication of patterned superomniphobic–superomniphilic surfaces is reported. Such patterned surfaces are expected to be useful in developing well-defined microreactors for liquid-phase reactions, significantly enhancing heat transfer during condensation and boiling of various low-surface-tension liquids, and in fabricating precisely tailored arrays of polymers and microparticles of different sizes and shapes.

    21. Magnetic Resonance Probes

      Design of a 13C Magnetic Resonance Probe Using a Deuterated Methoxy Group as a Long-Lived Hyperpolarization Unit (pages 10114–10117)

      Tomohiro Doura, Ryunosuke Hata, Dr. Hiroshi Nonaka, Prof. Kazuhiro Ichikawa and Prof. Shinsuke Sando

      Version of Record online: 7 SEP 2012 | DOI: 10.1002/anie.201202885

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      How to live longer: A fully deuterated 13C methoxy group (13CD3O) is presented as a new long-lived hyperpolarization unit for designing a sensitive 13C magnetic resonance probe. By utilizing the unit, a hyperpolarized magnetic resonance probe for sensing hypochlorous acid was successfully designed.

    22. Imaging Agents

      Near-Infrared Emitting Radioactive Gold Nanoparticles with Molecular Pharmacokinetics (pages 10118–10122)

      Chen Zhou, Dr. Guiyang Hao, Patrick Thomas, Dr. Jinbin Liu, Dr. Mengxiao Yu, Shasha Sun, Prof. Dr. Orhan K. Öz, Prof. Dr. Xiankai Sun and Prof. Dr. Jie Zheng

      Version of Record online: 7 SEP 2012 | DOI: 10.1002/anie.201203031

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      A molecular nanoprobe: Glutathione-coated near-infrared-emitting radioactive gold nanoparticles have been synthezised and behave like small-molecule contrast agents in pharmocokinetics. These nanoparticles show a rapid distribution half-life, a desirable elimination half-life, and hold promise for single-photon emission computed tomography (SPECT) and fluorescence imaging (see picture).

    23. Structure-Activity Relationship

      Effect of the Peptide Moiety of Lipid II on Bacterial Transglycosylase (pages 10123–10126)

      Hao-Wei Shih, Yi-Fan Chang, Wei-Jing Li, Fan-Chun Meng, Chia-Ying Huang, Dr. Che Ma, Dr. Ting-Jen R. Cheng, Prof. Dr. Chi-Huey Wong and Dr. Wei-Chieh Cheng

      Version of Record online: 5 SEP 2012 | DOI: 10.1002/anie.201204038

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      The writing's on the (cell) wall: A series of Lipid II analogues with modifications to the peptide moiety were evaluated as substrates of bacterial transglycosylase. The first two positions on the peptide, D-lactate and L-alanine (see scheme), especially their methyl groups, were found to be essential for substrate-binding activity, an important discovery for the design of antibiotics to inhibit cell-wall biosynthesis.

    24. Asymmetric Catalysis

      Homochiral Crystallization of Metal–Organic Silver Frameworks: Asymmetric [3+2] Cycloaddition of an Azomethine Ylide (pages 10127–10131)

      Xu Jing, Dr. Cheng He, Dapeng Dong, Linlin Yang and Prof. Chunying Duan

      Version of Record online: 7 SEP 2012 | DOI: 10.1002/anie.201204530

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      Enantiomeric silver-based MOFs were obtained through a homochiral crystallization of cinchonine and cinchonidine enantiomers as chiral adducts with silver. These MOFs exhibited excellent catalytic activity for asymmetric [3+2] cycloaddition (see scheme), giving products with high enantioselectivity.

    25. Protein Engineering

      Unnatural Amino Acid Mutagenesis of Fluorescent Proteins (pages 10132–10135)

      Dr. Feng Wang, Dr. Wei Niu, Prof. Jiantao Guo and Prof. Peter G. Schultz

      Version of Record online: 5 SEP 2012 | DOI: 10.1002/anie.201204668

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      Tyrosine 66 of a green fluorescent protein (GFP) was substituted with unnatural amino acids carrying boronate, azido, nitro, and keto substituents. In general, the equation imagevalues of these GFP mutants is blue-shifted relative to that of GFP, and the fluorescence intensity of the boronate variant increases upon oxidation (see scheme). The X-ray crystal structures of the keto and boronate GFP mutants provide explanations of their altered fluorescence properties.

    26. Polymerization in Frameworks

      Confined Polymerization in Porous Organic Frameworks with an Ultrahigh Surface Area (pages 10136–10140)

      Prof. Angiolina Comotti, Dr. Silvia Bracco, Martino Mauri, Sergio Mottadelli, Prof. Teng Ben, Prof. Shilun Qiu and Prof. Piero Sozzani

      Version of Record online: 5 SEP 2012 | DOI: 10.1002/anie.201205618

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      Polymers framed: Interpenetrated nanocomposites were formed by polymerization of acrylonitrile in a ultrahigh surface area (>5000 m2 g−1) porous framework. The resulting material realizes a hyperextended interface with uniform interdigitation of the two structures at the size limit of the individual molecular moieties. The confined poly(acrylonitrile) chains could be transformed into light-absorbing polyconjugated ladder polymers.

    27. Natural Products

      Potentially Biomimetic Total Synthesis and Relative Stereochemical Assignment of (±)-Gracilamine (pages 10141–10144)

      Songchuan Tian, Dr. Weiwei Zi and Prof. Dr. Dawei Ma

      Version of Record online: 7 SEP 2012 | DOI: 10.1002/anie.201205711

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      Gracil(e): The total synthesis of gracilamine features a potentially biomimetic intramolecular [3+2] cycloaddition to assemble its two fused five-membered rings and a debenzylation/ring-opening reaction to obtain the aldehyde intermediate (see scheme). The success of this synthesis provides a circumstantial evidence that supports the biosynthesis pathway of gracilamine proposed previously.

    28. Polymeric Heterojunction

      A Facile Band Alignment of Polymeric Carbon Nitride Semiconductors to Construct Isotype Heterojunctions (pages 10145–10149)

      Jinshui Zhang, Mingwen Zhang, Dr. Rui-Qing Sun and Prof. Xinchen Wang

      Version of Record online: 7 SEP 2012 | DOI: 10.1002/anie.201205333

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      Junction function: All-organic isotype heterojunctions are formed through the band alignment of polymeric carbon nitride semiconductors (CN and CNS, see scheme), improving the efficiency of charge separation and prolonging the lifetime of charge carriers. These polymeric heterostructures demonstrate an excellent performance for heterogeneous photocatalysis, as shown in a hydrogen-generation assay.

    29. Donor-Acceptor Systems

      You have full text access to this OnlineOpen article
      Isolable Phosphanylidene Phosphorane with a Sterically Accessible Two-Coordinate Phosphorus Atom (pages 10150–10153)

      Brian A. Surgenor, Prof. Michael Bühl, Prof. Alexandra M. Z. Slawin, Prof. J. Derek Woollins and Dr. Petr Kilian

      Version of Record online: 5 SEP 2012 | DOI: 10.1002/anie.201204998

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      'P' undressed: A stable phosphanylidene phosphorane with a sterically accessible (naked) two-coordinate P is reported (see structure). Coordination to Pd0 reveals its phosphine donor/phosphinidene acceptor (R3P[RIGHTWARDS ARROW]PR′) nature by exposing its phosphinidene-like reactivity.

    30. Multistable MOFs

      Hysteretic Three-Step Spin Crossover in a Thermo- and Photochromic 3D Pillared Hofmann-type Metal–Organic Framework (pages 10154–10158)

      Dr. Natasha F. Sciortino, Dr. Katrin R. Scherl-Gruenwald, Dr. Guillaume Chastanet, Dr. Gregory J. Halder, Dr. Karena W. Chapman, Prof. Jean-François Létard and Prof. Cameron J. Kepert

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/anie.201204387

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      Multistability is exhibited by a metal–organic framework material that undergoes unique three-step spin crossover with 20 K thermal hysteresis (see picture). The stepwise transition is coupled to a three-step structural transformation that defines four distinct structural states. The material also exhibits reversible photo-induced spin crossover.

    31. Rare Earths Redox Chemistry

      The Impact of Ligand Reorganization on Cerium(III) Oxidation Chemistry (pages 10159–10163)

      Jerome R. Robinson, Dr. Patrick J. Carroll, Prof. Patrick J. Walsh and Prof. Eric J. Schelter

      Version of Record online: 31 AUG 2012 | DOI: 10.1002/anie.201203481

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      Let's get cerium: The role of ligand organization in the redox chemistry of CeIII was investigated with a series of cerium(III)/alkali metal/1,1′-binolate (REMB) complexes. The electrochemical properties and chemical reactivity within the REMB framework are tunable through the choice of metal M, and the controlled redox behavior emphasizes the impact of ligand reorganization.

    32. Olefin Reduction

      Metal-free Catalytic Olefin Hydrogenation: Low-Temperature H2 Activation by Frustrated Lewis Pairs (pages 10164–10168)

      Lutz Greb, Dr. Pascual Oña-Burgos, Birgitta Schirmer, Prof. Dr. Stefan Grimme, Prof. Dr. Douglas W. Stephan and Dr. Jan Paradies

      Version of Record online: 31 AUG 2012 | DOI: 10.1002/anie.201204007

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      Weak nucleophiles for strong activation: The reversible activation of dihydrogen by an electron-deficient phosphine, (C6F5)PPh2, in combination with the Lewis acid B(C6F5)3 at −80 °C was accomplished. The catalytic hydrogenation of olefins proceeds through protonation and subsequent hydride attack. Electron-deficient phosphines and diarlyamines were demonstrated to be viable Lewis bases for the reaction, thus allowing catalyst loadings of 10 to 5 mol %.

    33. Photochemistry

      Synthesis of Fluorinated Tricyclic Scaffolds by Intramolecular [2+2] Photocycloaddition Reactions (pages 10169–10172)

      Dr. Diego A. Fort, Dr. Thomas J. Woltering, Dr. Matthias Nettekoven, Dr. Henner Knust and Prof. Dr. Thorsten Bach

      Version of Record online: 7 SEP 2012 | DOI: 10.1002/anie.201204080

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      Fabulous Fluorine: The synthesis of fluorinated products 1 and 2 by [2+2] photocycloaddition was readily feasible after optimization of the irradiation conditions. The electron-deficient trifluoroolefin unit reacted intramolecularly to products 1 (nine examples, d.r.>95:5). The reaction was also investigated after modification of position 2 of the side chain both with one or two fluoro substituents (e.g. to yield product 2).

    34. Group 12 Chemistry

      NHC-Stabilized Triorganozincates: Syntheses, Structures, and Transformation to Abnormal Carbene–Zinc Complexes (pages 10173–10176)

      Dr. Yuzhong Wang, Dr. Yaoming Xie, Mariham Y. Abraham, Robert J. Gilliard Jr., Dr. Pingrong Wei, Dr. Charles F. Campana, Prof. Dr. Henry F. Schaefer III, Prof. Dr. Paul von R. Schleyer and Prof. Dr. Gregory H. Robinson

      Version of Record online: 7 SEP 2012 | DOI: 10.1002/anie.201204712

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      Anion is superior: NHC-based triorganozincates, from mononuclear to trinuclear, have been synthesized. The NHC-based triorganozincate chain (see scheme; left) was transformed into an abnormal carbene (aNHC)-complexed zinc ring (right) by reaction with MeOTf, closing the aNHC-Group 12 complexes gap.

    35. Electrochemistry

      Nitroxide Radicals as Highly Reactive Redox Mediators in Dye-Sensitized Solar Cells (pages 10177–10180)

      Dr. Fumiaki Kato, Akitomo Kikuchi, Takumi Okuyama, Prof. Kenichi Oyaizu and Prof. Hiroyuki Nishide

      Version of Record online: 5 SEP 2012 | DOI: 10.1002/anie.201205036

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      Exchanged: The organic radical 2-azaadamantan-N-oxyl (AZA; see picture) is found to be a stable and highly reactive redox mediator in dye-sensitized solar cell (DSSC) electrolytes. This radical has an appropriate redox potential and significantly high values for the diffusivity, heterogeneous electron-transfer rate, and electron self-exchange reaction rate. In a DSSC the AZA-based electrolyte achieves an excellent photovoltaic performance.

    36. Asymmetric Hydrogenation

      Iridium-Catalyzed Asymmetric Hydrogenation of Pyridinium Salts (pages 10181–10184)

      Zhi-Shi Ye, Mu-Wang Chen, Qing-An Chen, Lei Shi, Ying Duan and Prof. Yong-Gui Zhou

      Version of Record online: 11 SEP 2012 | DOI: 10.1002/anie.201205187

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      Highly efficient iridium-catalyzed asymmetric hydrogenations of simple 2-substituted pyridinium salts gives the chiral 2-substituted piperidines with up to 93 % ee (see picture; cod=1,5-cyclooctadiene; synphos=(5,6),(5′,6′)-bis(ethylenedioxy)-2,2′-bis(diphenylphosphino)-1,1′-biphenyl). The key feature of this strategy is the activation of simple pyridines as the pyridinium salts, thus eliminating substrate inhibition and enhancing the reactivity.

    37. Total Synthesis

      Chemical Synthesis of a Heparan Sulfate Glycopeptide: Syndecan-1 (pages 10185–10189)

      Dr. Bo Yang, Dr. Keisuke Yoshida, Dr. Zhaojun Yin, Hang Dai, Herbert Kavunja, Dr. Mohammad H. El-Dakdouki, Suttipun Sungsuwan, Steven B. Dulaney and Prof. Dr. Xuefei Huang

      Version of Record online: 7 SEP 2012 | DOI: 10.1002/anie.201205601

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      Finishing first: The highly complex structure of the title compound (see picture) was assembled. The protective groups utilized, as well as the sequences for formation of the glycosyl linkages and protecting group removal are critical to the success of the synthesis. This first preparation of a heparan sulfate glycopeptide lays the foundation for accessing other members of this class of molecules.

    38. Iron Nanocatalysis

      In Situ Generated Iron Oxide Nanocrystals as Efficient and Selective Catalysts for the Reduction of Nitroarenes using a Continuous Flow Method (pages 10190–10193)

      Dr. David Cantillo, Dr. Mostafa Baghbanzadeh and Prof. Dr. C. Oliver Kappe

      Version of Record online: 5 SEP 2012 | DOI: 10.1002/anie.201205792

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      The best of both worlds: The benefits of homogeneous and heterogeneous nanocatalysis are combined, whereby highly reactive colloidal Fe3O4 nanocrystals are generated in situ that remain in solution long enough to allow the efficient and selective reduction of nitroarenes to anilines in continuous-flow mode (see scheme). After completion of the reaction, the nanoparticles aggregate and can be recovered by a magnet.

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