Angewandte Chemie International Edition

Cover image for Vol. 49 Issue 9

February 22, 2010

Volume 49, Issue 9

Pages 1509–1695

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. Cover Picture: AgIISO4: A Genuine Sulfate of Divalent Silver with Anomalously Strong One-Dimensional Antiferromagnetic Interactions (Angew. Chem. Int. Ed. 9/2010) (page 1509)

      Przemysław J. Malinowski, Mariana Derzsi, Zoran Mazej, Zvonko Jagličić, Bartłomiej Gaweł, Wiesław Łasocha and Wojciech Grochala

      Article first published online: 5 FEB 2010 | DOI: 10.1002/anie.201000368

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      Deep-black AgSO4 (Mr. Hyde) is a narrow-bandgap semiconductor and an extremely strong oxidant. W. Grochala and co-workers show in their Communication on page 1683 ff. that it differs in all important physicochemical properties from its lighter congener, unreactive colorless CuSO4 (Dr. Jekyll). Unusually strong antiferromagnetic coupling persists up to the temperature at which AgSO4 thermally decomposes (ca. 120 °C), which sets it apart from all other transition-metal sulfates.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. Inside Cover: Induced-Fit Binding of the Macrocyclic Noncovalent Inhibitor TMC435 to its HCV NS3/NS4A Protease Target (Angew. Chem. Int. Ed. 9/2010) (page 1510)

      Maxwell D. Cummings, Jimmy Lindberg, Tse-I Lin, Herman de Kock, Oliver Lenz, Elisabet Lilja, Sara Felländer, Vera Baraznenok, Susanne Nyström, Magnus Nilsson, Lotta Vrang, Michael Edlund, Åsa Rosenquist, Bertil Samuelsson, Pierre Raboisson and Kenneth Simmen

      Article first published online: 17 FEB 2010 | DOI: 10.1002/anie.201000389

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      The anti-HCV activity of TMC435, currently in phase 2b clinical studies as an HCV therapeutic (HCV=hepatitis C virus), is based on inhibition of the NS3/4A protease of the virus. As M. D. Cummings and co-workers describe in their Communication on page 1652 ff., binding of TMC435 to the target enzyme involves an induced fit, leading to occupancy of an extended S2 subsite. The authors thank J. M. Berke, E. Fransen, and L. Geeraert for assisting with the graphics.

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
  4. News

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
  5. Author Profile

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. Thomas Wirth (page 1528)

      Article first published online: 5 FEB 2010 | DOI: 10.1002/anie.200906959

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      “I chose chemistry as a career because I like to do experiments myself. Nowadays, this is unfortunately rarely the case. My biggest inspiration is a completely unexpected result from a seemingly straightforward experiment …” This and more about Anthony Thomas Wirth can be found on page 1528.

  6. Book Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. Protein Engineering Handbook. 2 volumes. Edited by Stefan Lutz and Uwe T. Bornscheuer. (page 1529)

      Peter Lindner

      Article first published online: 17 FEB 2010 | DOI: 10.1002/anie.200907322

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      Wiley-VCH, Weinheim 2008. 973 pp., hardcover € 349.00.—ISBN 978-3527318506

  7. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. Supported Membranes

      Metal-Organic Framework Membranes—High Potential, Bright Future? (pages 1530–1532)

      Jorge Gascon and Freek Kapteijn

      Article first published online: 2 FEB 2010 | DOI: 10.1002/anie.200906491

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      “Hard work today leads to success tomorrow” can be said for research on membranes of porous crystalline materials, which are ideal for size- and shape-selective separations with low energetic effort. The realization of the first metal-organic framework membranes may open up a plethora of applications, including functional coatings. The picture shows the separation of H2 and CO2 by a membrane on an alumina support.

    2. Microporous Materials

      Porous Organic Polymers: Distinction from Disorder? (pages 1533–1535)

      Abbie Trewin and Andrew I. Cooper

      Article first published online: 2 FEB 2010 | DOI: 10.1002/anie.200906827

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      An alternative explanation: The new microporous organic polymer framework PAF-1 displays exceptional physicochemical stability along with an extremely high surface area (BET surface area 5640 m2 g−1). The question arises whether this material displays the high degree of crystalline order presumed necessary for this high surface area.

  8. Essay

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. Hydrogen Generation

      Catalytic Aspects of Light-Induced Hydrogen Generation in Water with TiO2 and Other Photocatalysts: A Simple and Practical Way Towards a Normalization? (pages 1536–1539)

      Thomas Maschmeyer and Michel Che

      Article first published online: 25 JAN 2010 | DOI: 10.1002/anie.200903921

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      Avoiding erroneous conclusions: Only when operating under non-diffusion-limited conditions can statements be made regarding the inherent activity of a catalyst. Otherwise, such results reflect merely aspects of the reactor or reaction design. Suggestions are made as how to arrive at a more standardized method to overcome these problems.

  9. Review

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. Polymer Chemistry

      Thiol–Ene Click Chemistry (pages 1540–1573)

      Charles E. Hoyle and Christopher N. Bowman

      Article first published online: 17 FEB 2010 | DOI: 10.1002/anie.200903924

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      Click and easy: The radical thiol–ene reaction (see scheme) fulfills all the criteria for being a click reaction, and it has a unique potential for applications in polymer science and molecular synthesis. Particular advantages are simplicity, high yields and conversions, high reaction rates, and the possibility of photoinitiation.

  10. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. Book Review
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    12. Preview
    1. Quantum Dots

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      Water Splitting by Visible Light: A Nanophotocathode for Hydrogen Production (pages 1574–1577)

      Thomas Nann, Saad K. Ibrahim, Pei-Meng Woi, Shu Xu, Jan Ziegler and Christopher J. Pickett

      Article first published online: 5 FEB 2010 | DOI: 10.1002/anie.200906262

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      Hitting water with a 2 iron: A novel nanophotocathode for hydrogen production is based on a multilayer array of InP quantum dots activated with a synthetic diiron catalyst (see picture), which is related to the subsite of FeFe hydrogenase.

    2. Superconducting Carbides

      Superconductivity in Quasi One-Dimensional Carbides (pages 1578–1582)

      Wolfgang Scherer, Christoph Hauf, Manuel Presnitz, Ernst-Wilhelm Scheidt, Georg Eickerling, Volker Eyert, Rolf-Dieter Hoffmann, Ute C. Rodewald, Adrienne Hammerschmidt, Christian Vogt and Rainer Pöttgen

      Article first published online: 29 JAN 2010 | DOI: 10.1002/anie.200904956

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      The electronic structures of the isotypic carbides Sc3TC4 (see picture; T=Fe, Co, Ni) are investigated by theoretical and experimental charge-density studies. Even tiny differences in the electronic band structure of these solids are reflected in the properties of the Laplacian of the experimental electron density. Only the cobalt carbide is superconducting below 4.5 K and displays a structural phase transition around 70 K.

    3. Rearrangements

      Unexpected Electrophilic Rearrangements of Amides: A Stereoselective Entry to Challenging Substituted Lactones (pages 1583–1586)

      Claire Madelaine, Viviana Valerio and Nuno Maulide

      Article first published online: 2 FEB 2010 | DOI: 10.1002/anie.200906416

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      Surprise, surprise! An unexpected skeletal rearrangement was developed into a chemo- and stereoselective synthesis of α-allyl and allenyl lactones with challenging substitution patterns (see scheme; EWG=electron-withdrawing group). The generality, unique features, and synthetic potential of this reaction were probed and a mechanism was proposed.

    4. Heterocycles

      A Double Donor-Activated Ruthenium(VII) Catalyst: Synthesis of Enantiomerically Pure THF-Diols (pages 1587–1590)

      Huan Cheng and Christian B. W. Stark

      Article first published online: 1 FEB 2010 | DOI: 10.1002/anie.200903090

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      Double, double, no toil and trouble: Enantiomerically pure tetrahydrofurans are obtained with high position- and stereoselectivity through a ruthenium(VII)-catalyzed oxidative cyclization of 5,6-dihydroxy alkenes (see scheme TPAP=tetrapropylammonium perruthenate). A dual activation modifies the reactivity and increases the carbophilicity of the transition metal so that an otherwise unusual dioxygenation with perruthenate occurs.

    5. N2 Activation

      Photolysis of Aqueous [(NH3)5Os(μ-N2)Os(NH3)5]5+: Cleavage of Dinitrogen by an Intramolecular Photoredox Reaction (pages 1591–1593)

      Horst Kunkely and Arnd Vogler

      Article first published online: 4 FEB 2010 | DOI: 10.1002/anie.200905026

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      A quantum of light for nitrogen: An intramolecular photoredox reaction leads to the reductive cleavage of dinitrogen upon metal-to-ligand charge transfer (MLCT) excitation. The primary photochemical step is assumed to proceed by formation of an OsVI nitride complex (see scheme). Secondary reactions modify the product formation.

    6. Phosphorus Chemistry

      Shuttling P3 from Niobium to Rhodium: The Synthesis and Use of Ph3SnP3(C6H8) as a P3 Synthon (pages 1595–1598)

      Brandi M. Cossairt and Christopher C. Cummins

      Article first published online: 28 JAN 2010 | DOI: 10.1002/anie.200906633

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      Anatomy of a P3synthon: The Ph3SnP3(C6H8) molecule (see picture; Sn red, P orange) has been synthesized by triphosphorus transfer from a niobium complex. This molecule was shown to be a viable source of P3 in a proof-of-principle reaction: loss of Ph3SnCl and 1,3-cyclohexadiene from Ph3SnP3(C6H8) upon treatment with Wilkinson's catalyst, [ClRh(PPh3)3], gives rise to the new cyclo-P3 complex [(η3-P3)Rh(PPh3)3].

    7. Natural Product Synthesis

      Total Synthesis of (±)-Haliclonacyclamine C (pages 1599–1602)

      Brian J. Smith and Gary A. Sulikowski

      Article first published online: 2 FEB 2010 | DOI: 10.1002/anie.200905732

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      First in its class: The synthesis of the tetracyclic alkylpiperidine marine alkaloid (±)-haliclonacyclamine C has been completed, with a longest linear sequence of 24 steps. The key transformations are the stereoselective hydrogenation of an unsaturated macrocyclic bis(piperidine) and a ring-closing alkyne metathesis reaction.

    8. Solid-State Structures

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      Ferroelectricity in Perovskites with s0 A-Site Cations: Toward Near-Room-Temperature Multiferroics (pages 1603–1606)

      Erjun Kan, Hongjun Xiang, Changhoon Lee, Fang Wu, Jinlong Yang and Myung-Hwan Whangbo

      Article first published online: 1 FEB 2010 | DOI: 10.1002/anie.200905997

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      The origin of the ferroelectricity in the indium-based multiferroic perovskites (In1−xMx)MO3 (M=Mn0.5Fe0.5), and the question of how to lower their magnetic ordering (TN) and the ferroelectric Curie temperatures, was investigated by density functional calculations. The analyses explain why TN is near room temperature and why the perovskites with s0 and s2 A-site cations have similar ferroelectric distortions.

    9. Propargyl Amines

      A Versatile Synthetic Platform Based on Strained Propargyl Amines (pages 1607–1610)

      Zhi He and Andrei K. Yudin

      Article first published online: 29 JAN 2010 | DOI: 10.1002/anie.200906066

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      Divergent reactivity: Various ethynylaziridines behave as strained propargyl amines and can be directly converted into unprotected α-amino allenes by a highly diastereoselective SN2′ hydride delivery (see scheme). Additional reaction routes involve chemo- and regioselective transformation into either bicyclic aziridine/enol ethers or highly strained azirine alkynes.

    10. Domino Reactions

      Stereoselective One-Pot Synthesis of 1-Aminoindanes and 5,6-Fused Azacycles Using a Gold-Catalyzed Redox-Pinacol-Mannich-Michael Cascade (pages 1611–1614)

      Hyun-Suk Yeom, Youngun Lee, Jaewon Jeong, Eunsoo So, Soojin Hwang, Ji-Eun Lee, Shim Sung Lee and Seunghoon Shin

      Article first published online: 27 JAN 2010 | DOI: 10.1002/anie.200906346

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      Just another Mannich Monday: A cascade intramolecular redox-pinacol-Mannich-Michael reaction sequence catalyzed by gold complexes can be used to generate a variety of structures including spirocycles, 1-aminoindanes, and 5,6-fused azabicycles that have a quaternary carbon center. The reaction is characterized by complete atom-economy, high diastereoselectivity, and remarkable efficiency through tandem reactions.

    11. Microstructures

      Easy Synthesis of Hollow Polymer, Carbon, and Graphitized Microspheres (pages 1615–1618)

      An-Hui Lu, Wen-Cui Li, Guang-Ping Hao, Bernd Spliethoff, Hans-Josef Bongard, Bernd Bastian Schaack and Ferdi Schüth

      Article first published online: 29 JAN 2010 | DOI: 10.1002/anie.200906445

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      Balls galore! A new approach was developed for the easy synthesis of hollow microspheres with amorphous or graphitized microstructure. Starting from one type of solid polymer sphere, a simple water washing treatment led to the formation of hollow structures. Diverse products such as hollow carbon or graphitized spheres can be obtained, depending on subsequent treatment methods (see picture).

    12. Natural Products

      The Synthesis of Novel Disorazoles (pages 1619–1622)

      Romy Schäckel, Bettina Hinkelmann, Florenz Sasse and Markus Kalesse

      Article first published online: 22 JAN 2010 | DOI: 10.1002/anie.200906450

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      Big little brother: The simplified disorazole analogue 1 exhibits its cytotoxic activity at low nanomolar concentrations and provides selectivities not observed for the parent natural product.

    13. Single-Molecule Magnets

      A Liquid-Crystalline Single-Molecule Magnet with Variable Magnetic Properties (pages 1623–1626)

      Mathieu Gonidec, Fernando Luis, Àlex Vílchez, Jordi Esquena, David B. Amabilino and Jaume Veciana

      Article first published online: 27 JAN 2010 | DOI: 10.1002/anie.200905007

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      A terbium double-decker phthalocyanine complex has been prepared and characterized. The mesomorphism of the liquid-crystalline complex is used as a tool to reversibly adjust its magnetic properties, thus allowing the coexistence of two different relaxation processes, which can be reversibly modified by simple thermal treatments, to be observed.

    14. Biochemical Mechanisms

      Phosphorylation-Dependent Kinase–Substrate Cross-Linking (pages 1627–1630)

      Sujit Suwal and Mary Kay H. Pflum

      Article first published online: 27 JAN 2010 | DOI: 10.1002/anie.200905244

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      Pinning down kinase substrates: The identification of substrates of a particular kinase is fundamental to the elucidation of cell-signaling cascades. This problem has now been addressed by the title approach involving kinase-catalyzed labeling coupled with photo-cross-linking (see scheme). When coupled with mass spectrometry analysis, this strategy can be used to determine the sites of phosphorylation as well as the effector kinase. ADP=adenosine 5′-diphosphate.

    15. DNA Solutions

      Long-Term Structural and Chemical Stability of DNA in Hydrated Ionic Liquids (pages 1631–1633)

      Ranganathan Vijayaraghavan, Aleksey Izgorodin, Venkatraman Ganesh, Mahadevan Surianarayanan and Douglas R. MacFarlane

      Article first published online: 27 JAN 2010 | DOI: 10.1002/anie.200906610

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      Storage solutions: DNA is shown to be soluble in a variety of choline-based, hydrated ionic liquids (ILs; see picture). The IL-stored DNA molecules have exceptional long-term stability, in excess of one year.

    16. Synthetic Methods

      Catalytic Oxyamidation of Indoles (pages 1634–1637)

      Stéphane Beaumont, Valérie Pons, Pascal Retailleau, Robert H. Dodd and Philippe Dauban

      Article first published online: 28 JAN 2010 | DOI: 10.1002/anie.200906650

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      Twofold versatility: An efficient intermolecular oxyamidation of indoles relies on the application of rhodium(II)-catalyzed nitrene transfers. The cis or trans products are exclusively isolated in very good yields (up to 88 %) by changing the nucleophile. Control of the regioselectivity of the addition is also possible by modifying the substitution of the indole double bond (see scheme).

    17. Asymmetric Catalysis

      Chiral Tetrafluorobenzobarrelene Ligands for the Rhodium-Catalyzed Asymmetric Cycloisomerization of Oxygen- and Nitrogen-Bridged 1,6-Enynes (pages 1638–1641)

      Takahiro Nishimura, Takahiro Kawamoto, Makoto Nagaosa, Hana Kumamoto and Tamio Hayashi

      Article first published online: 1 FEB 2010 | DOI: 10.1002/anie.200906792

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      The long and winding Rhoad: The asymmetric cycloisomerization of nitrogen- and oxygen-bridged 1,6-enynes proceeded in the presence of a cationic rhodium complex that was coordinated by PPh3 and a chiral diene ligand to afford high yields of chiral 3-aza- and 3-oxabicyclo[4.1.0]heptenes and high enantioselectivities. TS=4-toluenesulfonyl, Tf=trifluoromethanesulfonyl.

    18. Fluoromethylation

      2-Fluoro-1,3-benzodithiole-1,1,3,3-tetraoxide: A Reagent for Nucleophilic Monofluoromethylation of Aldehydes (pages 1642–1647)

      Tatsuya Furukawa, Yosuke Goto, Jumpei Kawazoe, Etsuko Tokunaga, Shuichi Nakamura, Yudong Yang, Hongguang Du, Akikazu Kakehi, Motoo Shiro and Norio Shibata

      Article first published online: 29 JAN 2010 | DOI: 10.1002/anie.200906866

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      Matter of choice: The title compound (FBDT), a cyclic analogue of 1-fluorobis(phenylsulfonyl)methane (FBSM), was developed as a reagent for the nucleophilic monofluoromethylation of aldehydes. By choice of an appropriate base it is possible to achieve selective 1,2- or 1,4-addition of FBDT to conjugated aldehydes. The method was applied to the synthesis of a fluorinated isostere of osmundalactone.

    19. Synthetic Methods

      Stereoselective Ring Expansion of Vinyl Oxiranes: Mechanistic Insights and Natural Product Total Synthesis (pages 1648–1651)

      Matthew Brichacek, Lindsay A. Batory and Jon T. Njardarson

      Article first published online: 4 FEB 2010 | DOI: 10.1002/anie.200906830

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      What a (strain) relief! The first broadly applicable, catalytic, and stereoselective vinyl oxirane ring expansion is described (see scheme; hfacac=hexafluoroacetylacetonate). The stereoselectivity was influenced by several reaction parameters, and kinetic studies support a mechanistic proposal involving the in situ formation of a more reactive catalytic species. This ring-expansion reaction has been employed in the asymmetric total synthesis of (+)-goniothalesdiol.

    20. Enzyme Inhibitors

      Induced-Fit Binding of the Macrocyclic Noncovalent Inhibitor TMC435 to its HCV NS3/NS4A Protease Target (pages 1652–1655)

      Maxwell D. Cummings, Jimmy Lindberg, Tse-I Lin, Herman de Kock, Oliver Lenz, Elisabet Lilja, Sara Felländer, Vera Baraznenok, Susanne Nyström, Magnus Nilsson, Lotta Vrang, Michael Edlund, Åsa Rosenquist, Bertil Samuelsson, Pierre Raboisson and Kenneth Simmen

      Article first published online: 17 FEB 2010 | DOI: 10.1002/anie.200906696

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      If the shoe fits: TMC435, a noncovalent small-molecule inhibitor of the hepatitis C virus (HCV) NS3/NS4A protease, is currently undergoing clinical evaluation as an HCV therapeutic. In the crystal structure of the noncovalent NS3/NS4A protease–TMC435 complex the bound inhibitor exploits induced-fit binding. The new structure is consistent with the emerging view of viral resistance to NS3/NS4A protease inhibitors.

      Corrected by:

      Corrigendum: Corrigendum: Induced-Fit Binding of the Macrocyclic Noncovalent Inhibitor TMC435 to its HCV NS3/NS4A Protease Target

      Vol. 49, Issue 19, 3250, Article first published online: 20 APR 2010

    21. Heterogeneous Catalysis

      One-Pot Synthesis of Benzimidazoles by Simultaneous Photocatalytic and Catalytic Reactions on Pt@TiO2 Nanoparticles (pages 1656–1660)

      Yasuhiro Shiraishi, Yoshitsune Sugano, Shunsuke Tanaka and Takayuki Hirai

      Article first published online: 28 JAN 2010 | DOI: 10.1002/anie.200906573

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      Dual platinum action: A one-pot catalytic synthesis of benzimidazoles from the photoirradiation of an alcohol solution containing an ortho-arylenediamine and Pt@TiO2 nanoparticles is described. This reaction proceeded by the platinum-assisted photocatalytic oxidation of an alcohol and a catalytic dehydrogenation of the intermediates on the surface of platinum nanoparticles.

    22. Antitumor Agents

      Characterization of a Ruthenium(III)/NAMI-A Adduct with Bovine Serum Albumin that Exhibits a High Anti-Metastatic Activity (pages 1661–1664)

      Mimi Liu, Zhi Jun Lim, Yee Yen Gwee, Aviva Levina and Peter A. Lay

      Article first published online: 1 FEB 2010 | DOI: 10.1002/anie.200906079

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      An exchange for the better: X-ray absorption spectroscopic studies show that treatment of an RuIII drug, NAMI-A, with bovine serum albumin (BSA) results in complete replacement of the Cl and S-donor ligands with N-donor and carboxylato residues of the protein (see scheme). The RuIII–BSA adduct is as active in enhancing the cell–substrate interactions as the original NAMI-A complex (which converts into RuIII–BSA within minutes in the cell-culture medium).

    23. Artificial Vesicles

      Nanometer-Sized Fluorous Fullerene Vesicles in Water and on Solid Surfaces (pages 1665–1668)

      Tatsuya Homma, Koji Harano, Hiroyuki Isobe and Eiichi Nakamura

      Article first published online: 1 FEB 2010 | DOI: 10.1002/anie.200904659

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      A new twist for bucky balls: A fluorous fullerene amphiphile lacking the conventional polar head / nonpolar tail motif forms a vesicle in water (see picture, F green, C gray), mediated by the cohesive power of fullerene. The fluorous moiety covers the vesicle surface, and vesicle solutions dissolve perfluorooctane. Unlike lipid vesicles, the fluorous vesicle is very robust and retains its spherical shape even on a solid substrate under high vacuum.

    24. Molecular Rotors

      A Molecular Double Ball Bearing: An AgI–PtII Dodecanuclear Quadruple-Decker Complex with Three Rotors (pages 1669–1673)

      Shuichi Hiraoka, Yoshihiro Hisanaga, Motoo Shiro and Mitsuhiko Shionoya

      Article first published online: 29 JAN 2010 | DOI: 10.1002/anie.200905947

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      A marvelous machine: A 2.5 nm sized molecular machine that behaves like a double ball bearing with three rotors was constructed from two kinds of disk-shaped ligands, AgI ions, and dinuclear PtII bridging complexes (see structure: C red, N blue, O purple, S green, Ag yellow, Pt brown). Motion of the three rotors was found to depend greatly on the degree of interlocking between the two ligands in rotor 2 through helix inversion.

    25. Anion Recognition

      A Tridentate Halogen-Bonding Receptor for Tight Binding of Halide Anions (pages 1674–1677)

      Mohammed G. Sarwar, Bojan Dragisic, Sandeep Sagoo and Mark S. Taylor

      Article first published online: 29 JAN 2010 | DOI: 10.1002/anie.200906488

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      It′s in the I′s: Three suitably oriented electron-deficient iodoaryl groups form the basis for the first anion receptor (see structure; white H, gray C, red O, blue F, purple I, green Cl) that employs the halogen-bonding interaction alone to achieve high-affinity molecular recognition in dilute solution. The anion selectivity of this tridentate host differs from those of similar receptors based on hydrogen bonding.

    26. Curved π Diradical

      Three-Dimensional Intramolecular Exchange Interaction in a Curved and Nonalternant π-Conjugated System: Corannulene with Two Phenoxyl Radicals (pages 1678–1682)

      Akira Ueda, Shinsuke Nishida, Kozo Fukui, Tomoaki Ise, Daisuke Shiomi, Kazunobu Sato, Takeji Takui, Kazuhiro Nakasuji and Yasushi Morita 

      Article first published online: 27 JAN 2010 | DOI: 10.1002/anie.200906666

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      A neutral diradical based on corannulene with curved and nonalternant π conjugation has been synthesized and isolated as air-stable crystals. Sizable spin delocalization and strong intramolecular exchange interaction in the intrinsically three-dimensional π network (see picture), as well as significant diradical contributions in the ground state, were experimentally disclosed.

    27. Silver(II) Compounds

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      AgIISO4: A Genuine Sulfate of Divalent Silver with Anomalously Strong One-Dimensional Antiferromagnetic Interactions (pages 1683–1686)

      Przemysław J. Malinowski, Mariana Derzsi, Zoran Mazej, Zvonko Jagličić, Bartłomiej Gaweł, Wiesław Łasocha and Wojciech Grochala

      Article first published online: 18 JAN 2010 | DOI: 10.1002/anie.200906863

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      Black AgSO4, synthesized for the first time by a displacement reaction, differs considerably from anhydrous sulfates of its Group 11 congeners: it has a very small electronic band gap (ca. 0.2 eV) and an anomalously strong one-dimensional antiferromagnetic ordering ( J≈10 meV per Ag), which persists up to the onset of its thermal decomposition at about 120 °C. Ag gray, O red, S yellow.

    28. Cyanide Biosynthesis

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      [FeFe]-Hydrogenase Cyanide Ligands Derived From S-Adenosylmethionine-Dependent Cleavage of Tyrosine (pages 1687–1690)

      Rebecca C. Driesener, Martin R. Challand, Shawn E. McGlynn, Eric M. Shepard, Eric S. Boyd, Joan B. Broderick, John W. Peters and Peter L. Roach

      Article first published online: 27 JAN 2010 | DOI: 10.1002/anie.200907047

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      What's your poison? Hydrogenases catalyze the reversible formation of dihydrogen from two electrons and two protons. The maturation of the [FeFe]-hydrogenase active-site cofactor (H cluster) requires three gene products, HydE, HydF, and HydG. Cyanide has been characterized as one of the products of tyrosine cleavage by the S-adenosylmethionine-dependent enzyme HydG, clarifying its role in H-cluster biosynthesis. DOA=deoxyadenosine.

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    1. Preview: Angew. Chem. Int. Ed. 10/2010 (page 1695)

      Article first published online: 17 FEB 2010 | DOI: 10.1002/anie.201090023

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