Angewandte Chemie International Edition

Cover image for Angewandte Chemie International Edition

November 15, 2010

Volume 49, Issue 47

Pages 8765–9011

  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. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Cover Picture: The AlkB Domain of Mammalian ABH8 Catalyzes Hydroxylation of 5-Methoxycarbonylmethyluridine at the Wobble Position of tRNA (Angew. Chem. Int. Ed. 47/2010) (page 8765)

      Ye Fu, Dr. Qing Dai, Wen Zhang, Dr. Jin Ren, Prof. Tao Pan and Prof. Chuan He

      Article first published online: 12 OCT 2010 | DOI: 10.1002/anie.201003241

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      tRNA Hypermodification by mammalian ABH8 is described by C. He, T. Pan, and co-workers in their Communication on page 8885 ff. The mammalian AlkB homologue ABH8, containing an AlkB dioxygenase domain, catalyzes the oxidation of mcm5U into (S)-mchm5U at the wobble position (uridine) in tRNA.

  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. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Inside Cover: A Potent Trans-Diimine Platinum Anticancer Complex Photoactivated by Visible Light (Angew. Chem. Int. Ed. 47/2010) (page 8766)

      Dr. Nicola J. Farrer, Dr. Julie A. Woods, Dr. Luca Salassa, Yao Zhao, Kim S. Robinson, Dr. Guy Clarkson, Dr. Fiona S. Mackay and Prof. Peter J. Sadler

      Article first published online: 13 SEP 2010 | DOI: 10.1002/anie.201004988

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      Photoactivation can be used to activate anticancer drugs selectively just at the site of a tumor. Such targeted treatments promise fewer side effects and may address the problem of acquired resistance associated with drugs such as cisplatin. P. J. Sadler and co-workers show in their Communication on page 8905 ff. that the octahedral complex trans,trans,trans-[PtIV(N3)2(OH)2(py)2] is potentially cytotoxic towards a number of cell lines when activated by blue light, with no toxicity in the absence of irradiation.

  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. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Graphical Abstract: Angew. Chem. Int. Ed. 47/2010 (pages 8769–8781)

      Article first published online: 11 NOV 2010 | DOI: 10.1002/anie.201090149

  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. Minireview
    11. Review
    12. Communications
    13. 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. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Xiaoming Feng (page 8789)

      Article first published online: 8 OCT 2010 | DOI: 10.1002/anie.201005335

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      “My favorite subject at school was physics. When I wake up I wish I could fall asleep again …” This and more about Xiaoming Feng can be found on page 8789.

  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. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Chemistry in Motion. Reaction-Diffusion Systems for Micro- and Nanotechnology. By Bartosz A. Grzybowski. (page 8790)

      Michael Ibele

      Article first published online: 11 NOV 2010 | DOI: 10.1002/anie.201005949

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      John Wiley & Sons, Hoboken 2009. 302 pp., hardcover € 119.00.—ISBN 978-0470030431

  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. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Catenanes

      Bridging the Gap: Making the Link in Mechanically Interlocked Chiral Molecules (pages 8792–8794)

      Dr. Isabelle M. Dixon and Dr. Gwénaël Rapenne

      Article first published online: 21 SEP 2010 | DOI: 10.1002/anie.201003298

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      Open the bridge: A [2]catenane has been synthesized around a salt-bridge template (see picture). Addition and sequestration of Zn2+ ions or variation of the pH value can reversibly trigger the formation and rupture of the salt bridge, thus inducing a major reorganization within the molecule. Suggestions as to the use of such systems as molecular logic gates or nanomechanical devices are made.

    2. Genome Sequencing

      The Development of DNA Sequencing: From the Genome of a Bacteriophage to That of a Neanderthal (pages 8795–8797)

      Uschi Sundermann, Dr. Susanna Kushnir and Prof. Dr. Frank Schulz

      Article first published online: 22 SEP 2010 | DOI: 10.1002/anie.201003880

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      Them bones gonna rise again: Only a few weeks ago the Neandertal genome, deciphered from small amounts of ancient DNA, was published. This mileston was possible thanks to tremendous improvements in DNA-sequencing technologies. The picture shows a bone fragment from which genomic DNA was isolated for the sequencing experiment. (Picture copyright: Max-Planck-Institute of Evolutionary Anthropology).

  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. Minireview
    11. Review
    12. Communications
    13. Preview
    1. N-Heterocyclic Carbenes

      The Beginnings of N-Heterocyclic Carbenes (pages 8798–8801)

      Prof. Dr. Wolfgang Kirmse

      Article first published online: 18 AUG 2010 | DOI: 10.1002/anie.201001658

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      A long time in the waiting: In 1960 Wanzlick brought N-heterocyclic carbenes to the point of take off. Experimental shortcomings, misunderstanding, and prejudgments, however, hindered their take off. Only 30 years later, with the isolation and structural elucidation of N-heterocyclic carbenes by Arduengo, did the flight begin.

  9. Minireview

    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. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Isoprenoid Biosynthesis

      Reductive Dehydroxylation of Allyl Alcohols by IspH Protein (pages 8802–8809)

      Dr. Tobias Gräwert, Ingrid Span, Prof. Dr. Dr. Adelbert Bacher and Prof. Dr. Michael Groll

      Article first published online: 4 OCT 2010 | DOI: 10.1002/anie.201000833

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      The way forward: In the last two decades a novel biosynthetic route to isopentenyl diphosphate and dimethylallyl diphosphate, the non-mevalonate or deoxyxylulose pathway, has been elucidated. The IspH protein (see space-filling model) catalyzes the terminal step of this biosynthetic pathway. The enzymes of this pathway are absent in mammals and are validated targets for new antibiotics.

  10. 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. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Stable Cyclic Carbenes

      Stable Cyclic Carbenes and Related Species beyond Diaminocarbenes (pages 8810–8849)

      Dr. Mohand Melaimi, Dr. Michèle Soleilhavoup and Prof. Guy Bertrand

      Article first published online: 10 SEP 2010 | DOI: 10.1002/anie.201000165

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      A big family: Neutral carbon-based ligands are not restricted to classical cyclic diaminocarbenes (NHCs). Several other types of cyclic carbenes are stable and act as strong electron donors (see picture). Cyclic bent allenes (CBAs), carbodiphosphoranes (CCDPs), and vinylidenephosphorane (CVP) can even behave as four-electron donors. The gamut of electronic and steric properties available makes carbon ligands strong competitors to the phosphorus family.

  11. 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. Minireview
    11. Review
    12. Communications
    13. Preview
    1. Catalytic C[BOND]H Functionalization

      Catalytic C[BOND]H Amination with Unactivated Amines through Copper(II) Amides (pages 8850–8855)

      Stefan Wiese, Dr. Yosra M. Badiei, Raymond T. Gephart, Dr. Susanne Mossin, Dr. Matthew S. Varonka, Dr. Marie M. Melzer, Prof. Dr. Karsten Meyer, Prof. Thomas R. Cundari and Prof. Timothy H. Warren

      Article first published online: 15 SEP 2010 | DOI: 10.1002/anie.201003676

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      En route to catalysis: Two equivalents of the three-coordinate copper(II) amide [(Cl2NN)Cu]-NHAd participate in stoichiometric C[BOND]H amination by a H-atom abstraction/radical capture sequence. This active species may be generated through a copper(II) tert-butoxide intermediate to allow for the unprecedented catalytic amination of sp3-C[BOND]H bonds with unactivated alkylamines. This method greatly expands the range of amines for catalytic C[BOND]H amination since most protocols require N-based electron-withdrawing groups.

    2. Continuous-Flow Reactors

      Real-Time Product Switching Using a Twin Catalyst System for the Hydrogenation of Furfural in Supercritical CO2 (pages 8856–8859)

      James G. Stevens, Dr. Richard A. Bourne, Dr. Martyn V. Twigg and Prof. Martyn Poliakoff

      Article first published online: 6 OCT 2010 | DOI: 10.1002/anie.201005092

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      “Vending machine” chemistry: A tandem flow-reactor setup can be used to generate a choice of five products in high yield from a single biorenewable feedstock, furfural (1). “Real-time” switching to any of the products can be achieved rapidly by simply changing the reactor conditions.

    3. Synthetic Methods

      You have full text access to this OnlineOpen article
      A Simple and General Platform for Generating Stereochemically Complex Polyene Frameworks by Iterative Cross-Coupling (pages 8860–8863)

      Suk Joong Lee, Thomas M. Anderson and Prof. Martin D. Burke

      Article first published online: 6 OCT 2010 | DOI: 10.1002/anie.201004911

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      Not so complex: A novel iterative cross-coupling strategy provides access to useful building blocks that enable the simple preparation of complex polyene natural-product motifs in all possible stereoisomeric forms. The method was used to synthesize the polyene core of vacidin A (see structure).

    4. Molecular Aggregates

      Halide-Directed Assembly of Multicomponent Systems: Highly Ordered AuI–AgI Molecular Aggregates (pages 8864–8866)

      Dr. Igor O. Koshevoy, Dr. Antti J. Karttunen, Julia R. Shakirova, Dr. Alexei S. Melnikov, Prof. Matti Haukka, Prof. Sergey P. Tunik and Prof. Tapani A. Pakkanen

      Article first published online: 8 OCT 2010 | DOI: 10.1002/anie.201004386

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      Triangular cationic belts [Au3{PPh2(C6H4)nPPh2}3]3+ enclose bimetallic clusters [AuwAgx(C2Ph)yXz] in molecular aggregates obtained by halide (X)-directed assembly of multicomponent systems. The largest aggregate consists of a central metal alkynyl halide cluster [Au18Ag30(C2Ph)36Cl9]3+ inside a [Au3{PPh2(C6H4)5PPh2}3]3+ belt and comprises 51 metal atoms (see picture; Ag green, Au yellow, Cl violet, P red).

    5. Mesoporous Crystals

      Self-Consistent Structural Solution of Mesoporous Crystals by Combined Electron Crystallography and Curvature Assessment (pages 8867–8871)

      Dr. Keiichi Miyasaka and Prof. Osamu Terasaki

      Article first published online: 12 OCT 2010 | DOI: 10.1002/anie.201003875

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      Pore and wall structures for ordered mesoporous crystalline materials can be obtained from electron crystallographic reconstruction based on transmission electron micrographs (see picture; left). Curvature and surface properties are then used to determine the mesostructures in a self-consistent manner within the data (right: color-coded distributions of Gaussian curvature on a surface viewed along [111]).

    6. Sensors

      Detection of Ethylene Gas by Fluorescence Turn-On of a Conjugated Polymer (pages 8872–8875)

      Dr. Birgit Esser and Prof. Dr. Timothy M. Swager

      Article first published online: 6 OCT 2010 | DOI: 10.1002/anie.201003899

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      Ripe fruits: The fluorescence of a conjugated polymer is quenched by the presence of copper(I) moieties. Upon exposure to ethylene gas the copper complexes bind to ethylene and no longer quench the polymer fluorescence (see picture). This sensory concept can be used in solution and in thin films.

    7. Metal–Organic Frameworks

      Urothermal Synthesis of Crystalline Porous Materials (pages 8876–8879)

      Dr. Jian Zhang, Julia T. Bu, Dr. Shumei Chen, Tao Wu, Dr. Shoutian Zheng, Yigang Chen, Ruben A. Nieto, Prof. Dr. Pingyun Feng and Prof. Dr. Xianhui Bu

      Article first published online: 15 OCT 2010 | DOI: 10.1002/anie.201003900

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      Pores from urea: Urea derivatives are shown to be a highly versatile solvent system for the synthesis of crystalline solids. In particular, reversible binding of urea derivatives to framework metal sites has been utilized to create a variety of materials that integrate both porosity and open metal sites (see picture).

    8. Nanotechnology

      Tunable Nanosynthesis of Composite Materials by Electron-Impact Reaction (pages 8880–8884)

      Laurent Bernau, Dr. Mihai Gabureac, Dr. Rolf Erni and Dr. Ivo Utke

      Article first published online: 8 OCT 2010 | DOI: 10.1002/anie.201004220

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      Impact factor: Electron-impact dissociation reactions in two-adsorbate systems were tuned by applying specific exposure conditions in electron microscopes. Pulsed electron-impact exposure could drive the dissociation reaction of one of the adsorbates into the molecule-limited regime while the reaction of the other adsorbate continued in the electron-limited regime. The pulse period gave control over the composition of the deposit (see scheme).

    9. RNA Modification

      The AlkB Domain of Mammalian ABH8 Catalyzes Hydroxylation of 5-Methoxycarbonylmethyluridine at the Wobble Position of tRNA (pages 8885–8888)

      Ye Fu, Dr. Qing Dai, Wen Zhang, Dr. Jin Ren, Prof. Tao Pan and Prof. Chuan He

      Article first published online: 11 NOV 2010 | DOI: 10.1002/anie.201001242

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      Family ties: The AlkB family of nonheme iron, α-ketoglutarate (αKG)-dependent dioxygenases is involved in biological processes such as DNA/RNA repair and obesity. The AlkB domain of ABH8 is shown to catalyze the hydroxylation of a modified uridine (mcm5U) into (S)-mchm5U at the wobble position of the anticodon stem–loop in tRNA (see scheme), thereby suggesting that this protein is a tRNA hypermodification enzyme.

    10. Crystal Precursors

      Proto-Calcite and Proto-Vaterite in Amorphous Calcium Carbonates (pages 8889–8891)

      Dr. Denis Gebauer, Dr. Philips N. Gunawidjaja, Dr.  J. Y. Peter Ko, Dr. Zoltán Bacsik, Baroz Aziz, Lijia Liu, Dr. Yongfeng Hu, Prof. Lennart Bergström, Dr. Cheuk-Wai Tai, Prof. Tsun-Kong Sham, Dr. Mattias Edén and Dr. Niklas Hedin

      Article first published online: 14 OCT 2010 | DOI: 10.1002/anie.201003220

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      Amorphous order: Amorphous calcium carbonates (ACC) have an intrinsic structure relating to the crystalline polymorphs of calcite and vaterite. The proto-crystalline structures of calcite and vaterite (pc-ACC and pv-ACC) are analyzed by NMR (see picture), IR, and EXAFS spectroscopy, which shows that the structuring of ACC relates to the underlying pH-dependent equilibria.

    11. Noncovalent Interactions

      Mechanistic Insights into a Gas–Solid Reaction in Molecular Crystals: The Role of Hydrogen Bonding (pages 8892–8896)

      Dr. Guillermo Mínguez Espallargas, Dr. Jacco van de Streek, Dr. Philippe Fernandes, Prof. Alastair J. Florence, Dr. Michela Brunelli, Dr. Kenneth Shankland and Prof. Lee Brammer

      Article first published online: 11 OCT 2010 | DOI: 10.1002/anie.201003265

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      Hydrogen bonding leads the way: Reaction of nonporous crystalline coordination compound 1 with HCl gas results in conversion into the crystalline salt 2 (see picture) following chemisorption and insertion of HCl into Cu[BOND]N bonds. Powder diffraction studies show that [CuBr2Cl2]2− ions formed in 2 are reoriented to maximize the strength of hydrogen bonds and halogen bonds by preferentially involving Cl rather than Br ligands as acceptor sites.

    12. Drug Delivery

      Nanoparticle-Mediated Delivery of Bleomycin (pages 8897–8901)

      Thomas Georgelin, Dr. Sophie Bombard, Dr. Jean-Michel Siaugue and Prof. Valérie Cabuil

      Article first published online: 7 OCT 2010 | DOI: 10.1002/anie.201003316

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      Direct delivery: Multifunctionalized magnetic nanoparticles, which are highly stable and positively charged, induce strong interactions with cells and nuclei, thus confining bleomycin (BLM) close to its DNA target (see picture; PEG=polyethylene glycol). Grafted BLM can induce significant damage in DNA and cancerous cells.

    13. Graphene Oxide Frameworks

      Graphene Oxide Framework Materials: Theoretical Predictions and Experimental Results (pages 8902–8904)

      Dr. Jacob W. Burress, Dr. Srinivas Gadipelli, Dr. Jamie Ford, Dr. Jason M. Simmons, Dr. Wei Zhou and Prof. Taner Yildirim

      Article first published online: 8 OCT 2010 | DOI: 10.1002/anie.201003328

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      A promising storage medium for hydrogen and other gases is a graphene oxide framework (GOF) that consists of layers of GO connected by benzene-1,4-diboronic acid (B14DBA) pillars (see picture). Theoretical predictions and the initial experimental results are presented for this cheap and environmentally friendly building block for nanoporous materials with better gas adsorption properties.

    14. Photoactivated Prodrugs

      A Potent Trans-Diimine Platinum Anticancer Complex Photoactivated by Visible Light (pages 8905–8908)

      Dr. Nicola J. Farrer, Dr. Julie A. Woods, Dr. Luca Salassa, Yao Zhao, Kim S. Robinson, Dr. Guy Clarkson, Dr. Fiona S. Mackay and Prof. Peter J. Sadler

      Article first published online: 11 NOV 2010 | DOI: 10.1002/anie.201003399

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      Activating platinum with light: An inert platinum(IV) diazido complex trans, trans,trans-[Pt(N3)2(OH)2(py)2] becomes potently cytotoxic to cancer cells when activated by low doses of visible light.

    15. Elliptical Nanotubules

      Differential Ion Exchange in Elliptical Uranyl Diphosphonate Nanotubules (pages 8909–8911)

      Pius O. Adelani and Prof. Dr. Thomas E. Albrecht-Schmitt

      Article first published online: 12 OCT 2010 | DOI: 10.1002/anie.201004797

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      Nanotubular bells: A simple route to a uranyl diphosphonate with an elliptical nanotubular structure has been developed (see picture; C black, O red, Cs blue, F yellow, UO7 green pentagonal bipyramids, phosphonate violet tetrahedra). The interior of the nanotubules provides a different chemical environment than the exterior with regards to the exchange of Cs+ cations for Ag+ cations, thus demonstrating that uranyl nanotubules are functional materials.

    16. Molecular Capsules

      A Molecular Capsule Network: Guest Encapsulation and Control of Diels–Alder Reactivity (pages 8912–8914)

      Dr. Yasuhide Inokuma, Shota Yoshioka and Prof. Dr. Makoto Fujita

      Article first published online: 6 OCT 2010 | DOI: 10.1002/anie.201004781

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      The time capsule: A variety of guest molecules are stably trapped in networked coordination capsules up to 200 °C, which is above the boiling points of the guests. Networked capsules provide a distinctly different environment in the crystal form relative to that of pores, and are suitable for storing reactive molecules: Cyclopentadiene remains a monomer within the capsule even after heating, whereas dimerization through a Diels–Alder reaction takes place within the pore.

    17. Chiral Anions

      A Chiral-Anion Generator: Application to Catalytic Desilylative Kinetic Resolution of Silyl-Protected Secondary Alcohols (pages 8915–8917)

      Hailong Yan, Hyeong Bin Jang, Ji-Woong Lee, Hong Ki Kim, Prof. Dr. Soon Won Lee, Prof. Dr. Jung Woon Yang and Prof. Dr. Choong Eui Song

      Article first published online: 6 OCT 2010 | DOI: 10.1002/anie.201004777

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      Getting the grips on fluoride: Chiral hydroxy-terminated polyethers bearing a 3,3′-halogen-substituted chiral 1,1′-bi-2-naphthol (BINOL) unit manifest a new structural motif for chiral-anion generators. Their unique properties are revealed through highly enantioselective desilylative kinetic resolution of a variety of silyl-protected racemic alcohols with KF (see scheme).

    18. Cross-Coupling

      A Mild and Efficient Palladium-Catalyzed Cyanation of Aryl Mesylates in Water or tBuOH/Water (pages 8918–8922)

      Pui Yee Yeung, Dr. Chau Ming So, Prof. Dr. Chak Po Lau and Prof. Dr. Fuk Yee Kwong

      Article first published online: 8 OCT 2010 | DOI: 10.1002/anie.201005121

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      Cool and compatible: Aryl mesylates and tosylates underwent palladium-catalyzed cyanation under mild, aqueous conditions at 65–80 °C (see scheme). In many cases, water could be used as the reaction medium without a cosolvent, and a variety of substituents R, such as keto, aldehyde, ester, free amine, and nitrile groups, remained intact during the transformation. Cy=cyclohexyl, Ms=methanesulfonyl, Ts=p-toluenesulfonyl.

    19. Cryptands

      Oxidatively Stable, Aqueous Europium(II) Complexes through Steric and Electronic Manipulation of Cryptand Coordination Chemistry (pages 8923–8925)

      Nipuni-Dhanesha H. Gamage, Dr. Yujiang Mei, Joel Garcia and Prof. Matthew J. Allen

      Article first published online: 6 OCT 2010 | DOI: 10.1002/anie.201002789

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      A series of cryptands has been prepared and they demonstrate the relationship between oxidative stability of aqueous EuII and ligand properties (see figure). One of these EuII complexes is more stable than FeII in hemoglobin and appears to be the most oxidatively-stable aqueous EuII species known. The high stability of EuII is expected to enable the use of the unique magnetic and optical properties of this ion in vivo.

    20. Reaction Mechanisms

      Mechanism of Thermal Reversal of the (Fulvalene)tetracarbonyldiruthenium Photoisomerization: Toward Molecular Solar–Thermal Energy Storage (pages 8926–8929)

      Dr. Yosuke Kanai, Dr. Varadharajan Srinivasan, Dr. Steven K. Meier, Prof. Dr. K. Peter C. Vollhardt and Prof. Jeffrey C. Grossman

      Article first published online: 14 OCT 2010 | DOI: 10.1002/anie.201002994

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      A closer look at the title reaction pinpoints a surprising mechanism—a relatively rapid preequilibrium between cyclopentadienyl complex 2 and fulvalene diradical complex 1 precedes the rate-determining antisyn rotation and formation of the Ru[BOND]Ru bond. The computed energy values agree well with all experimental data, including saturation kinetics for the trapping of the intermediate by CCl4. TS=transition state.

    21. Multicomponent Reactions

      Three-Component Coupling Reactions of Silyl Glyoxylates, Vinyl Grignard Reagent, and Nitroalkenes: An Efficient, Highly Diastereoselective Approach to Nitrocyclopentanols (pages 8930–8933)

      Gregory R. Boyce and Dr. Jeffrey S. Johnson

      Article first published online: 14 OCT 2010 | DOI: 10.1002/anie.201003470

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      Quick and easy: A regio- and stereoselective three-component coupling reaction generates functionalized (Z)-silyl enol ethers through a vinylation/[1,2]-Brook rearrangement/vinylogous Michael reaction cascade. These adducts can then undergo a diastereoselective deprotection/intramolecular Henry sequence to rapidly assemble densely functionalized nitrocyclopentanols with three contiguous stereocenters (see scheme; TES=triethylsilyl).

    22. Water Oxidation

      Chemical and Light-Driven Oxidation of Water Catalyzed by an Efficient Dinuclear Ruthenium Complex (pages 8934–8937)

      Dr. Yunhua Xu, Dr. Andreas Fischer, Lele Duan, Lianpeng Tong, Erik Gabrielsson, Prof. Björn Åkermark and Prof. Licheng Sun

      Article first published online: 12 OCT 2010 | DOI: 10.1002/anie.201004278

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      Here splits the sun: A dinuclear ruthenium complex has been synthesized and employed to catalyze the homogeneous water oxidation (see picture; purple Ru, green Cl, blue N, red O). An exceptionally high turnover number was observed both for chemical (CeIV as the oxidant) and light-driven ([Ru(bpy)3]2+-type photosensitizers) water splitting.

    23. Rhodium Catalysis

      Linear-Selective Rhodium(I)-Catalyzed Addition of Arylboronic Acids to Allyl Sulfones (pages 8938–8941)

      Gavin C. Tsui and Prof. Dr. Mark Lautens

      Article first published online: 12 OCT 2010 | DOI: 10.1002/anie.201004345

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      One step further: The rhodium(I)-catalyzed addition of readily available arylboronic acids to allyl sulfones affords the linear (formal) hydroarylated products in good yields and excellent regioselectivities. The reaction broadens the scope of unactivated alkenes that can participate in rhodium-catalyzed addition reactions.

    24. Supramolecular Metal Drug

      Noncovalent DNA-Binding Metallo-Supramolecular Cylinders Prevent DNA Transactions in vitro (pages 8942–8945)

      Cosimo Ducani, Anna Leczkowska, Dr. Nikolas J. Hodges and Prof. Michael J. Hannon

      Article first published online: 8 OCT 2010 | DOI: 10.1002/anie.201004471

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      Supramolecular metal cylinders not only bind noncovalently to DNA inducing substantial coiling but are able to recognize specific DNA structures involved in biological processes as DNA replication. It is demonstrated that these molecules can inhibit the amplification of the DNA mediated by a Taq DNA polymerase and are even able to displace the enzyme from a double strand DNA (see scheme).

    25. C[BOND]H Functionalization

      A General Catalyst for the β-Selective C–H Bond Arylation of Thiophenes with Iodoarenes (pages 8946–8949)

      Kirika Ueda, Shuichi Yanagisawa, Dr. Junichiro Yamaguchi and Prof. Dr. Kenichiro Itami

      Article first published online: 8 OCT 2010 | DOI: 10.1002/anie.201005082

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      Open access: The normally less-reactive β position of thiophenes was previously inaccessible to direct functionalization. However, the β selectivity observed with the catalytic system PdCl2/P{OCH(CF3)2}3/Ag2CO3 in the arylation of thiophenes with iodoarenes (see scheme) is a remarkably general phenomenon applicable to unsubstituted, monosubstituted, and disubstituted thiophene derivatives, as well as thiophene-containing fused aromatic compounds.

    26. Single-Nucleotide Polymorphism

      Real-Time SNP Analysis in Secondary-Structure-Folded Nucleic Acids (pages 8950–8953)

      Jeffrey Grimes, Dr. Yulia V. Gerasimova and Dr. Dmitry M. Kolpashchikov

      Article first published online: 20 OCT 2010 | DOI: 10.1002/anie.201004475

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      A tricomponent sensor was designed for genotyping stem-loop-structured DNA sequences. DNA adaptor strand f (see picture; red) hybridizes to the analyte (orange) with high affinity and unwinds its secondary structure; strand m (green) forms a stable complex only with the fully complementary analyte sequence. A fluorescing molecular beacon reports complex formation.

    27. Biomass Conversion

      Mechanism of Glucose Isomerization Using a Solid Lewis Acid Catalyst in Water (pages 8954–8957)

      Dr. Yuriy Román-Leshkov, Dr. Manuel Moliner, Dr. Jay A. Labinger and Prof. Mark E. Davis

      Article first published online: 20 OCT 2010 | DOI: 10.1002/anie.201004689

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      Other way round: 1H and 13C NMR spectroscopy on isotopically labeled glucose reveals that in the presence of tin-containing zeolite Sn-Beta, the isomerization reaction of glucose in water proceeds by way of an intramolecular hydride shift (see scheme) rather than proton transfer. This is the first mechanistic demonstration of Sn-Beta acting as a Lewis acid in a purely aqueous environment.

    28. Lanthanide Silanimines

      Dehydrosilylation of ArNHSiH3 with Ytterbium(II) Amide: Formation of a Dimeric Ytterbium(II) Silanimine Complex (pages 8958–8961)

      Yang Chen, Dr. Haibin Song and Prof. Dr. Chunming Cui

      Article first published online: 7 OCT 2010 | DOI: 10.1002/anie.201004856

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      Agostic silanimine complexes: Reaction of [Yb{N(SiMe3)2}2(thf)2] with ArNHSiH3 resulted in the formation of the first lanthanide silanimine complex [{ArNSiH[N(SiMe3)2]}2Yb2] (see picture), having a planar Yb2Si2 core with significant α-(SiH)⋅⋅⋅Yb interactions, as well as the monomeric homoleptic lanthanide(II) amide [{ArNSiH2[N(SiMe3)2]}2Yb], showing β-agostic (SiH)⋅⋅⋅Yb interactions.

    29. Domino Reactions

      Heteroatom-Nucleophile-Induced C[BOND]C Fragmentations: Synthesis of Allenes and Entry to Domino Reactions (pages 8962–8965)

      Tanguy Saget and Dr. Nicolai Cramer

      Article first published online: 6 OCT 2010 | DOI: 10.1002/anie.201004795

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      Blessed are the piece-makers: Heteroatom nucleophiles (NuH) induce Grob-type fragmentations of vinyl triflates under mild conditions and provide ω-allene-functionalized carboxylic acid derivatives. These products are a versatile starting point for domino and one-pot reactions accessing a range of structurally diverse scaffolds in good yields.

    30. Hyperhalogens

      Hyperhalogens: Discovery of a New Class of Highly Electronegative Species (pages 8966–8970)

      Mary Willis, Matthias Götz, Prof. Dr. Anil K. Kandalam, Prof. Dr. Gerd F. Ganteför and Prof. Dr. Puru Jena

      Article first published online: 6 OCT 2010 | DOI: 10.1002/anie.201002212

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      Hyper trumps super: A central atom, typically a metal, surrounded by halogen or oxygen atoms is called a superhalogen. Theoretical calculations and experiments reveal that a new class of highly electronegative species can be created when the central metal atom is surrounded by superhalogen moieties. These hyperhalogens can have electron affinities even larger than those of their superhalogen building blocks.

    31. Histidine Phosphorylation

      Detection and Identification of Protein-Phosphorylation Sites in Histidines through HNP Correlation Patterns (pages 8971–8974)

      Sebastian Himmel, Sebastian Wolff, Dr. Stefan Becker, Dr. Donghan Lee and Prof. Dr. Christian Griesinger

      Article first published online: 11 OCT 2010 | DOI: 10.1002/anie.201003965

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      Three not of a kind: A NMR HNP experiment can distinguish between all three possible single- and double-phosphorylated histidines without requiring pKa or chemical shift information (see picture). The method is tested on phosphorylated histidines and phosphocarrier protein HPr. It detects phosphorylation in phosphotransferase system regulation domain I (PRDI).

    32. Boron-Centered Radicals

      The Reduction Chemistry of Ferrocenylborole (pages 8975–8978)

      Prof. Dr. Holger Braunschweig, Prof. Dr. Frank Breher, Dr. Ching-Wen Chiu, Daniela Gamon, Dominik Nied and Dr. Krzysztof Radacki

      Article first published online: 12 OCT 2010 | DOI: 10.1002/anie.201003611

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      Time to B radical: One-electron reduction of 1-ferrocenyl-2,3,4,5-tetraphenylborole results in a radical anion with 5 π electrons in the borole ring. Both EPR spectroscopic investigations and spin density calculations confirm the formation of a borol radical (see picture). Further reduction stimulates an intramolecular [(C5H5)Fe] migration from the cyclopentadienyl anion to the borole dianion.

    33. Ylide Chemistry

      A Direct Ylide Transfer to Carbonyl Derivatives and Heteroaromatic Compounds (pages 8979–8983)

      Dr. Xueliang Huang, Dr. Richard Goddard and Dr. Nuno Maulide

      Article first published online: 11 OCT 2010 | DOI: 10.1002/anie.201002919

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      Power transfer: The title reaction proceeds under mild conditions (room temperature, short reaction times) and directly affords sulfonium ylides from active methylene compounds and heteroaromatics in a single step and in high yields. A detailed comparative structural analysis of a variety of ylides is presented and the implications of structure on the reactivity of these compounds are discussed.

    34. Asymmetric Hydroamination

      Asymmetric Intermolecular Hydroamination of Unactivated Alkenes with Simple Amines (pages 8984–8987)

      Alexander L. Reznichenko, Hiep N. Nguyen and Prof. Dr. Kai C. Hultzsch

      Article first published online: 11 OCT 2010 | DOI: 10.1002/anie.201004570

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      A hard nut to crack: The asymmetric intermolecular Markovnikov addition of simple amines to unactivated alkenes can be achieved utilizing binaphtholate rare-earth-metal catalysts with up to 61 % ee and 73 % de in the case where R2 contains a stereogenic center.

    35. Ligand Design

      Recyclable Catalysts for Palladium-Catalyzed C[BOND]O Coupling Reactions, Buchwald–Hartwig Aminations, and Sonogashira Reactions (pages 8988–8992)

      Andreas Dumrath, Xiao-Feng Wu, Dr. Helfried Neumann, Dr. Anke Spannenberg, Dr. Ralf Jackstell and Prof. Dr. Matthias Beller

      Article first published online: 15 OCT 2010 | DOI: 10.1002/anie.201001787

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      Simply reuse: Homogeneous palladium catalysts are effective and attractive tools for advanced organic synthesis (see example). Compound 1 belongs to a new class of ligands that enable recycling of the precious-metal catalyst directly from the reaction without any heterogenization.

    36. Hydrogen Generation

      ortho-Metalation of Iron(0) Tribenzylphosphine Complexes: Homogeneous Catalysts for the Generation of Hydrogen from Formic Acid (pages 8993–8996)

      Albert Boddien, Felix Gärtner, Dr. Ralf Jackstell, Dr. Henrik Junge, Dr. Anke Spannenberg, Dr. Wolfgang Baumann, Prof. Dr. Ralf Ludwig and Prof. Dr. Matthias Beller

      Article first published online: 15 OCT 2010 | DOI: 10.1002/anie.201004621

      Thumbnail image of graphical abstract

      Without noble metals: A new catalyst derived from a non-noble metal has been developed for the selective generation of hydrogen from formic acid. DFT calculations and NMR spectroscopy support the formation of active ortho-metalated iron species as key intermediates during catalysis.

    37. Laves Phases

      Structural Topology and Chemical Bonding in Laves Phases (pages 8997–9001)

      Dr. Alim Ormeci, Prof. Dr. Arndt Simon and Prof. Yuri Grin

      Article first published online: 7 OCT 2010 | DOI: 10.1002/anie.201001534

      Thumbnail image of graphical abstract

      A combined analysis of the electron localizability indicator (ELI; see isosurface ELI for TiBe2) and electron density, the characteristic structural motif of the Laves phases MN2 was shown to be mainly stabilized by charge transfer from M to N. In different groups of Laves phases, the bonding situation ranges from multicenter bonds between M and N atoms to the formation of Nδ− polyanions.

    38. Eight-Connected Silicon

      Unusual Silicon Connectivities in the Binary Compounds GdSi5, CeSi5, and Ce2Si7 (pages 9002–9006)

      Dr. Aron Wosylus, Katrin Meier, Dr. Yurii Prots, Dr. Walter Schnelle, Dr. Helge Rosner, Dr. Ulrich Schwarz and Prof. Yuri Grin

      Article first published online: 15 OCT 2010 | DOI: 10.1002/anie.201003490

      Thumbnail image of graphical abstract

      Under high-pressure high-temperature conditions, the title compounds with 4, 5, 6, or 8 Si[BOND]Si contacts are formed. The interatomic distances can be scaled to the number of homonuclear neighbors in the silicide framework. Analysis of the chemical bonding reveals multicenter bonds between metal and Si atoms (see figure for CeSi5: Si blue and green, Ce red) and a contribution of semi-core states (the penultimate shell) of Ce to the chemical bonding.

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      Article first published online: 11 NOV 2010 | DOI: 10.1002/anie.201090150

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