Angewandte Chemie International Edition

Cover image for Vol. 50 Issue 38

September 12, 2011

Volume 50, Issue 38

Pages 8761–8991

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. Corrigendum
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Cover Picture: Efficient Entry to the Hasubanan Alkaloids: First Enantioselective Total Syntheses of (−)-Hasubanonine, (−)-Runanine, (−)-Delavayine, and (+)-Periglaucine B (Angew. Chem. Int. Ed. 38/2011) (page 8761)

      Dr. Seth B. Herzon, Nicholas A. Calandra and Sandra M. King

      Article first published online: 16 AUG 2011 | DOI: 10.1002/anie.201105017

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      A unified synthetic strategy to prepare four hasubanan alkaloids, including hasubanonine (depicted), is described by S. B. Herzon et al. in their Communication on page 8863 ff. The synthesis features the application of 5-trimethylsilylcyclopentadiene as a removable, stabilizing stereocontrol element. This controlling group serves to set the absolute configuration in the products and is thermally cleaved at approximately 80 °C lower than the parent cyclopentadiene adducts.

  2. Inside Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. Corrigendum
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Inside Cover: Direct Conductance Measurement of Individual Metallo-DNA Duplexes within Single-Molecule Break Junctions (Angew. Chem. Int. Ed. 38/2011) (page 8762)

      Song Liu, Prof. Dr. Guido H. Clever, Dr. Yusuke Takezawa, Motoo Kaneko, Prof. Dr. Kentaro Tanaka, Prof. Dr. Xuefeng Guo and Prof. Dr. Mitsuhiko Shionoya

      Article first published online: 30 AUG 2011 | DOI: 10.1002/anie.201104818

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      DNA-based hybrid materials when integrated into nanodevices can serve as conductive biocompatible bridges that may interface electronic circuits with biological systems. As X. Guo, M. Shionoya, and co-workers report in their Communication on page 8886 ff, the electrical conductance of individual metallo-DNA duplexes bridging a carbon nanotube gap can be measured and switched by use of Cu2+ ions.

  3. Back Cover

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. Corrigendum
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Back Cover: Tuning DNA Stability To Achieve Turnover in Template for an Enzymatic Ligation Reaction (Angew. Chem. Int. Ed. 38/2011) (page 8762)

      Abu Kausar, Rosalie D. McKay, Jade Lam, Rohan S. Bhogal, Alexandra Y. Tang and Prof. Julianne M. Gibbs-Davis

      Article first published online: 16 AUG 2011 | DOI: 10.1002/anie.201104919

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      Unlike native DNA a DNA template containing a destabilizing modification dissociates from the templated ligation product after its formation. As reported by J. M. Gibbs-Davis et al. in their Communication on page 8922 ff., such destabilizing templates turn over in enzymatic ligation reactions, thereby leading to multiple strands per template. Consequently, isothermal DNA amplification and even replication can be achieved using ligase, simple destabilizing modifications, and standard DNA functional groups.

  4. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. Corrigendum
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Graphical Abstract: Angew. Chem. Int. Ed. 38/2011 (pages 8765–8776)

      Article first published online: 8 SEP 2011 | DOI: 10.1002/anie.201190077

  5. Corrigendum

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. Corrigendum
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. You have free access to this content
      Corrigendum: Primary and Secondary Aminophosphines as Novel P-Stereogenic Building Blocks for Ligand Synthesis (page 8776)

      Marc Revés, Dr. Catalina Ferrer, Thierry León, Sean Doran, Dr. Pablo Etayo, Dr. Anton Vidal-Ferran, Prof. Antoni Riera and Prof. Xavier Verdaguer

      Article first published online: 8 SEP 2011 | DOI: 10.1002/anie.201190078

      This article corrects:

      Primary and Secondary Aminophosphines as Novel P-Stereogenic Building Blocks for Ligand Synthesis

      Vol. 49, Issue 49, 9452–9455, Article first published online: 26 OCT 2010

  6. News

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. Corrigendum
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Michael J. Krische (page 8782)

      Article first published online: 16 AUG 2011 | DOI: 10.1002/anie.201103730

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      “My favorite place on earth is with friends and family. The greatest scientific advance in the next decade will be the union of directed evolution and metal catalysis. …” This and more about Michael J. Krische can be found on page 8782.

  8. News

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

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. Corrigendum
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. The Art of Process Chemistry. Edited by Nobuyoshi Yasuda. (pages 8784–8785)

      Hans-Jürgen Federsel

      Article first published online: 2 AUG 2011 | DOI: 10.1002/anie.201103165

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      Wiley-VCH, Weinheim 2010. 282 pp., hardcover € 119.00.—ISBN 978-3527324705

  10. Highlights

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. Corrigendum
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Total Synthesis

      Total Synthesis of Bryostatin 1: A Short Route (pages 8786–8789)

      Dr. Soraya Manaviazar and Prof. Dr. Karl J. Hale

      Article first published online: 12 JUL 2011 | DOI: 10.1002/anie.201101562

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      A chemical legacy: Keck and his team have chemically pursued the bryostatin 1 structure with great vigor in recent years and, in late 2010, they finally completed their quest of developing a short and efficient total synthesis of this complex natural product (see structure). The present Highlight provides a brief but nevertheless detailed overview of the Keck synthesis and its chemical legacy in terms of new reactions.

    2. Catalytic Processes

      Towards Direct Mukaiyama-Type Reactions Catalytic in Silicon (pages 8790–8792)

      Prof. Dr. Jesús M. García, Prof. Dr. Mikel Oiarbide and Prof. Dr. Claudio Palomo

      Article first published online: 8 JUL 2011 | DOI: 10.1002/anie.201102423

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      Direct catalytic enolate generation from unactivated carboxylic acid derivatives may provide new routes for asymmetric carbon–carbon bond formation (see scheme). Recent studies demonstrate the potential of silicon catalysts or promoters in this endeavor, and this is best illustrated by a Mannich-type reaction of simple amides.

  11. Minireview

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. Corrigendum
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Clicking Biomacromolecules

      Reliable and Efficient Procedures for the Conjugation of Biomolecules through Huisgen Azide–Alkyne Cycloadditions (pages 8794–8804)

      Dr. Enrique Lallana, Prof. Ricardo Riguera and Prof. Eduardo Fernandez-Megia

      Article first published online: 17 AUG 2011 | DOI: 10.1002/anie.201101019

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      Efficient and benign bioconjugation: CuI-catalyzed azide–alkyne cycloaddition (CuAAC) is an established coupling method because of its high reliability and straightforward experimental procedure. However, the Cu catalyst has often proved detrimental to proteins, nucleic acids, and polysaccharides. CuI ligands and Cu-free strain-promoted procedures (SPAAC) have been developed that are efficient and avoid degradation of the resulting bioconjugates.

  12. Review

    1. Top of page
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    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. Corrigendum
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Staudinger Ligation

      Staudinger Ligation as a Method for Bioconjugation (pages 8806–8827)

      Dr. Sander S. van Berkel, Mark B. van Eldijk and Prof. Dr. Jan C. M. van Hest

      Article first published online: 2 SEP 2011 | DOI: 10.1002/anie.201008102

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      Phosphorus and azides have a high affinity for one another. This discovery has led to the development of various phosphorus-containing bioconjugation probes. At present, traceless, nontraceless, and phosphite Staudinger ligation probes are frequently applied. The current status of their utilization in life sciences and materials science is described in this Review.

  13. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Cover
    4. Back Cover
    5. Graphical Abstract
    6. Corrigendum
    7. News
    8. Author Profile
    9. News
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    15. Preview
    1. Polyazides

      Preparation and Characterization of the Binary Group 13 Azides M(N3)3 and M(N3)3⋅CH3CN (M=Ga, In, Tl), [Ga(N3)5]2−, and [M(N3)6]3− (M=In, Tl) (pages 8828–8833)

      Prof. Dr. Ralf Haiges, Dr. Jerry A. Boatz, Jodi M. Williams and Prof. Dr. Karl O. Christe

      Article first published online: 15 JUL 2011 | DOI: 10.1002/anie.201103101

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      Proceed with caution: The use of fluoride starting materials and SO2 as a solvent yields neat triazides M(N3)3 (M=Ga, In, Tl), thus firmly establishing the existence of thallium triazide. In CH3CN, the new M(N3)3⋅CH3CN donor–acceptor adducts were obtained. Reactions of the triazides with tetraphenylphosphonium azide in CH3CN yields exclusively the novel [Ga(N3)5]2−, [In(N3)6]3− and [Tl(N3)6]3− anions (see picture, M green, N blue).

    2. Conducting Layered Materials

      Rb4Sn5P4Se20: A Semimetallic Selenophosphate (pages 8834–8838)

      Dr. In Chung, Dr. Kanishka Biswas, Dr. Jung-Hwan Song, Dr. John Androulakis, Dr. Konstantinos Chondroudis, Prof. Konstantinos M. Paraskevopoulos, Prof. Arthur J. Freeman and Prof. Mercouri G. Kanatzidis

      Article first published online: 2 AUG 2011 | DOI: 10.1002/anie.201104050

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      Moonlight metal: The valence-precise compound Rb4Sn5P4Se20 (see picture, Rb blue, Sn green, P black, Se red) is the first metallic selenophosphate. It features a new structure hybrid of “conducting” [Sn5Se8] layers and “insulating” [P2Se6] ligands. It shows the highest electrical conductivity among the chalcophosphates and an extremely low thermal conductivity of 0.44 W m−1 K−1 at room temperature.

    3. Non-Innocent Ligands

      Developing Synthetic Approaches with Non-Innocent Metalloligands: Easy Access to IrI/Pd0 and IrI/Pd0/IrI Cores (pages 8839–8843)

      Dr. Cristina Tejel, Laura Asensio, Dr. M. Pilar del Río, Dr. Bas de Bruin, Dr. José A. López and Prof. Dr. Miguel A. Ciriano

      Article first published online: 17 AUG 2011 | DOI: 10.1002/anie.201104045

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      Guilty as charged is the verdict for anionic Ir complex [Ir(bpa−2 H)(cod)] in its reactions with PdII compounds. The net transfer of two electrons from the Ir complex to Pd allows easy preparation of di- and trinuclear π-imine-coordinated Pd0 compounds such as [{Ir(PyCH2NCHPy)(cod)}2Pd] (see picture; C white, Ir red, N blue, Pd yellow). bpa−2 H: doubly deprotonated form of N,N-bis(2-picolyl)amine (bpa); cod: 1,5-cyclooctadiene.

    4. Asymmetric Synthesis

      Highly Enantioselective Synthesis of Axially Chiral Biarylphosphonates: Asymmetric Suzuki–Miyaura Coupling Using High-Molecular-Weight, Helically Chiral Polyquinoxaline-Based Phosphines (pages 8844–8847)

      Dr. Takeshi Yamamoto, Yuto Akai, Dr. Yuuya Nagata and Prof. Dr. Michinori Suginome

      Article first published online: 4 AUG 2011 | DOI: 10.1002/anie.201103792

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      Taking a new turn: An asymmetric Suzuki–Miyaura coupling of 1-bromo-2-naphthalenephosphonic esters with o-methyl-substituted phenylboronic acids proceeds with high enantioselectivity in the presence of high-molecular-weight helically chiral polyquinoxaline-based phosphines (PQXphos) bearing pendant diarylphosphino groups.

    5. Graphene

      Claisen Rearrangement of Graphite Oxide: A Route to Covalently Functionalized Graphenes (pages 8848–8852)

      Dr. William R. Collins, Wiktor Lewandowski, Ezequiel Schmois, Dr. Joseph Walish and Prof. Dr. Timothy M. Swager

      Article first published online: 8 AUG 2011 | DOI: 10.1002/anie.201101371

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      On the GO: The basal plane allylic alcohol functionality of graphite oxide (GO) can be converted into N,N-dimethylamide groups through an Eschenmoser–Claisen sigmatropic rearrangement by using N,N-dimethylacetamide dimethyl acetal. Subsequent saponification of these groups affords the carboxylic acids (see picture), which, when deprotonated, electrostatically stabilize the graphene sheets in an aqueous environment.

    6. Drug Delivery

      pH-Tunable Calcium Phosphate Covered Mesoporous Silica Nanocontainers for Intracellular Controlled Release of Guest Drugs (pages 8853–8857)

      Hwa Pyeong Rim, Kyung Hyun Min, Hong Jae Lee, Prof. Dr. Seo Young Jeong and Prof. Dr. Sang Cheon Lee

      Article first published online: 8 AUG 2011 | DOI: 10.1002/anie.201101536

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      Springing the trap: A pH-responsive mesoporous silica nanoparticle with a calcium phosphate (CaP) pore-blocking coating was developed by enzyme-mediated surface mineralization under mild conditions. Upon exposure to cellular lysosomal pH, guest anticancer drug was released from the pore by dissolution of the CaP pore blocker (see picture; HAp=hydroxyapatite).

    7. Metal–Organic Frameworks

      Porous Indium–Organic Frameworks and Systematization of Structural Building Blocks (pages 8858–8862)

      Dr. Shou-Tian Zheng, Jennifer J. Bu, Tao Wu, Chengtsung Chou, Prof. Dr. Pingyun Feng and Prof. Dr. Xianhui Bu

      Article first published online: 16 AUG 2011 | DOI: 10.1002/anie.201101957

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      The indium family tree: The discovery of an elusive dimeric indium cluster together with super-trimeric indium clusters in five porous indium–organic frameworks reveals the systematics of indium-based building blocks and their cooperative and competitive roles in the crystallization of chiral and achiral porous frameworks. One of these materials has the smallest possible charge-balancing organic cation and a very high Langmuir surface area.

    8. Natural Products Synthesis

      Efficient Entry to the Hasubanan Alkaloids: First Enantioselective Total Syntheses of (−)-Hasubanonine, (−)-Runanine, (−)-Delavayine, and (+)-Periglaucine B (pages 8863–8866)

      Dr. Seth B. Herzon, Nicholas A. Calandra and Sandra M. King

      Article first published online: 3 JUN 2011 | DOI: 10.1002/anie.201102226

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      Maximized divergence: The hasubanan alkaloids given in the scheme have been synthesized in eight or nine steps from the aryl azide 1. The utility of 5-trimethylsilylcyclopentadiene as an easily removed, stabilizing stereocontrol element has been demonstrated.

    9. Porphyrinoids

      Palladium-Catalyzed β-Selective Direct Arylation of Porphyrins (pages 8867–8870)

      Yu Kawamata, Sumito Tokuji, Prof. Dr. Hideki Yorimitsu and Prof. Dr. Atsuhiro Osuka

      Article first published online: 3 JUN 2011 | DOI: 10.1002/anie.201102318

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      Four birds with one stone: A palladium catalyst/potassium carbonate/pivalic acid system enables direct arylation of porphyrins by aryl bromides (see scheme; Ar′=3,5-tBu2C6H3). The C[BOND]H arylation shows excellent β selectivity and does not require porphyrin prefunctionalization, hence representing an extremely efficient method for rapidly providing a series of new β-arylated porphyrins.

    10. Mass Spectrometry

      Observing the Hierarchical Self-Assembly and Architectural Bistability of Hybrid Molecular Metal Oxides Using Ion-Mobility Mass Spectrometry (pages 8871–8875)

      Dr. Johannes Thiel, Dongmei Yang, Mali H. Rosnes, Xiuli Liu, Carine Yvon, Stephanie E. Kelly, Dr. Yu-Fei Song, Dr. De-Liang Long and Prof. Leroy Cronin

      Article first published online: 16 AUG 2011 | DOI: 10.1002/anie.201102340

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      Ion-mobility mass spectrometry has been explored as a new technique in the analysis of polyoxometalates and was utilized for the differentiation between photoswitchable isomers of organic–inorganic hybrid compounds (see picture).

    11. Nanocrystal Catalysts

      Atomic-Distribution-Dependent Electrocatalytic Activity of Au–Pd Bimetallic Nanocrystals (pages 8876–8880)

      Jong Wook Hong, Dongheun Kim, Young Wook Lee, Minjung Kim, Shin Wook Kang and Prof. Sang Woo Han

      Article first published online: 2 AUG 2011 | DOI: 10.1002/anie.201102578

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      In the mix: Au–Pd alloy, Au@Pd core–shell, Pd, and Au nanocrystals (NCs) with an identical octahedral shape and with similar NC size were prepared to examine exclusively the effect of atomic distribution on the catalytic performance of NCs (see picture). The catalytic activities and stabilities toward formic acid oxidation highly depend on the atomic distribution in the NCs: Au–Pd alloy > Au@Pd core–shell > Pd ≫ Au NCs.

    12. Crystallization

      On the Nature of Chirality Imparted to Achiral Polymers by the Crystallization Process (pages 8881–8885)

      Dr. Martin Rosenthal, Dr. Georg Bar, Dr. Manfred Burghammer and Dr. Dimitri A. Ivanov

      Article first published online: 25 AUG 2011 | DOI: 10.1002/anie.201102814

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      Twisted crystals: Upon crystallization, achiral polymers can form chiral crystalline lamellae, such as right- and left-handed helicoids. The chiral parameter imparted by crystallization is the chain tilt with respect to the lamellar normal. Thus, lamella having crystalline stems tilted to the right from the normal to the basal plane will form right-handed helicoids, and vice versa.

    13. Electrical Conductance

      Direct Conductance Measurement of Individual Metallo-DNA Duplexes within Single-Molecule Break Junctions (pages 8886–8890)

      Song Liu, Prof. Dr. Guido H. Clever, Dr. Yusuke Takezawa, Motoo Kaneko, Prof. Dr. Kentaro Tanaka, Prof. Dr. Xuefeng Guo and Prof. Dr. Mitsuhiko Shionoya

      Article first published online: 14 JUL 2011 | DOI: 10.1002/anie.201102980

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      Bridging the gap: The electrical conductance of individual metallo-DNA duplexes that bridge a carbon nanotube gap can be measured and switched by use of Cu2+ ions (see picture, yellow sphere: Cu2+). These studies form the basis for new exciting research that interfaces molecular nanodevices with biological systems.

    14. Actinides

      Bonding Changes in Plutonium(III) and Americium(III) Borates (pages 8891–8894)

      Matthew J. Polinski, Shuao Wang, Dr. Evgeny V. Alekseev, Prof. Dr. Wulf Depmeier and Prof. Dr. Thomas E. Albrecht-Schmitt

      Article first published online: 18 AUG 2011 | DOI: 10.1002/anie.201103502

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      A matter of size: A dramatic change occurs between the reactivity of PuIII and AmIII centers in molten boric acid. The resulting complexes display different inner-sphere ligands and different coordination environments (see Pu[B4O6(OH)2Cl] and Am[B9O13(OH)4]⋅H2O in the picture).

    15. Synthetic Methods

      Combinatorial Catalysis Employing a Visible Enzymatic Beacon in Real Time: Synthetically Versatile (Pseudo)Halometalation/Carbocyclizations (pages 8895–8899)

      Jacob A. Friest, Sylvain Broussy, Woo Jin Chung and Prof. David B. Berkowitz

      Article first published online: 16 AUG 2011 | DOI: 10.1002/anie.201103365

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      For the big screen: An alcohol oxidase/peroxidase-based screen for combinatorial catalysis produces a signal in the visible region and in real time. A targeted high-throughput screen uncovered a bromometalation/carbocyclization route to bicyclic terpenoid cores and a thiocyano palladation/carbocyclization for the ready installation of vinyl thiocyanates.

    16. Fluorination in Flow

      Accelerating Palladium-Catalyzed C[BOND]F Bond Formation: Use of a Microflow Packed-Bed Reactor (pages 8900–8903)

      Dr. Timothy Noël, Dr. Thomas J. Maimone and Prof. Dr. Stephen L. Buchwald

      Article first published online: 11 AUG 2011 | DOI: 10.1002/anie.201104652

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      A flow process for Pd-catalyzed C[BOND]F bond formation is described. A microreactor with a packed-bed design allows for easy handling of large quantities of insoluble CsF with precise control over reaction times, efficient mixing, and the ability to safely handle elevated temperatures and pressures. A variety of aryl triflates, including heteroaryl ones, were converted into aryl fluorides in short reaction times (see scheme).

    17. Synthetic Methods

      Anion Relay Chemistry: Access to the Type II ARC Reaction Manifold through a Fundamentally Different Reaction Pathway Exploiting 1-Oxa-2-silacyclopentanes and Related Congeners (pages 8904–8907)

      Prof. Dr. Amos B. Smith III, Dr. Rongbiao Tong, Dr. Won-Suk Kim and Dr. William A. Maio

      Article first published online: 10 AUG 2011 | DOI: 10.1002/anie.201103886

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      Distinctly different: Two 1-oxa-2-silacyclopentenes and a saturated congener have been synthesized and demonstrated to provide access to type II anion relay chemistry (ARC) through a fundamentally new mechanistic pathway. Similar to previous studies, but contrary to initial hypothesis, Brook rearrangement additives (hexamethylphosphoramide and CuI) are necessary to promote Si migration and anion capture.

    18. Boron Ligands

      Extending the Chain: Synthetic, Structural, and Reaction Chemistry of a BN Allenylidene Analogue (pages 8908–8911)

      Dr. Jochen Niemeyer, David A. Addy, Ian Riddlestone, Michael Kelly, Dr. Amber L. Thompson, Dr. Dragoslav Vidovic and Prof. Simon Aldridge

      Article first published online: 11 AUG 2011 | DOI: 10.1002/anie.201103757

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      α versus γ: [CpFe(CO)(PCy3)(BNCMes2)]+, synthesized by halide abstraction, represents the first example of a BN allenylidene analogue, and features an unsaturated MBNC π system. Although DFT calculations show significant LUMO amplitude at the γ (carbon) position, primary reactivity towards nucleophiles occurs at the sterically less hindered α (boron) center.

    19. Heterogeneous Catalysis

      Influence of Methyl Halide Treatment on Gold Nanoparticles Supported on Activated Carbon (pages 8912–8916)

      Dr. Jacinto Sá, Dr. Alexandre Goguet, S. F. Rebecca Taylor, Ramchandra Tiruvalam, Prof. Christopher J. Kiely, Dr. Maarten Nachtegaal, Prof. Graham J. Hutchings and Prof. Christopher Hardacre

      Article first published online: 10 AUG 2011 | DOI: 10.1002/anie.201102066

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      Catalyzing concept: Methyl halides have been used to disperse large (around 20 nm) gold nanoparticles supported on carbon into dispersed gold atoms/dimers at low temperature and atmospheric pressure (see picture). The process occurs through the progressive removal of gold–halogen entities from the metal nanoparticles and a gradual decrease in the size of the gold nanoparticles on the minute timescale.

    20. Highly Efficient Amide Synthesis from Alcohols and Amines by Virtue of a Water-Soluble Gold/DNA Catalyst (pages 8917–8921)

      Ye Wang, Dapeng Zhu, Lin Tang, Dr. Sujing Wang and Prof. Zhiyong Wang

      Article first published online: 16 AUG 2011 | DOI: 10.1002/anie.201102374

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      Gold takes to water: The synthesis of amides directly from alcohols and amines was realized by using a water-soluble Au/DNA nanohybrid as the catalyst. The interactions between the gold nanoparticles, DNA, and water lead to high catalytic efficiency under mild reaction conditions. The wide substrate scope includes less-basic aromatic amines, and this catalyst is recyclable.

    21. Engineering DNA Turnover

      Tuning DNA Stability To Achieve Turnover in Template for an Enzymatic Ligation Reaction (pages 8922–8926)

      Abu Kausar, Rosalie D. McKay, Jade Lam, Rohan S. Bhogal, Alexandra Y. Tang and Prof. Julianne M. Gibbs-Davis

      Article first published online: 17 AUG 2011 | DOI: 10.1002/anie.201102579

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      Learning to let go: Introducing destabilizing modifications into a DNA template leads to turnover in a DNA-templated ligation reaction. By incorporating a cross-catalytic cycle, self-replication was also achieved, with one target able to make 32 copies of itself (see picture). This destabilization approach represents a general method for incorporating amplification into DNA ligation processes using T4 DNA ligase.

    22. Palladium Catalysis

      Palladium-Catalyzed Tunable Functionalization of Allylic Imidates: Regioselective Aminodiacetoxylation and Aziridination (pages 8927–8930)

      Dr. Sunliang Cui, Dr. Lukasz Wojtas and Prof. Dr. Jon C. Antilla

      Article first published online: 10 AUG 2011 | DOI: 10.1002/anie.201103500

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      In control: The title reaction has been shown to be highly general and efficient, thus exhibiting valuable potential synthetic utility (see scheme; DMF=N,N-dimethylformamide). Isotope labeling and two proposed mechanistic pathways, which invoke a PdII/PdIV catalytic cycle, show divergent C[BOND]N and C[BOND]O bond formation.

    23. Synthetic Methods

      Intermolecular and Selective Synthesis of 2,4,5-Trisubstituted Oxazoles by a Gold-Catalyzed Formal [3+2] Cycloaddition (pages 8931–8935)

      Dr. Paul W. Davies, Alex Cremonesi and Dr. Lidia Dumitrescu

      Article first published online: 26 JUL 2011 | DOI: 10.1002/anie.201103563

      Thumbnail image of graphical abstract

      Oxazole new world: A gold-catalyzed intermolecular reaction of pyridine-N-aminides with ynamides can be used to prepare trisubstituted 1,3-oxazoles with a variety of functional groups. This formal [3+2] cycloaddition employs robust conjugated N-ylides as N-nucleophilic N-acyl nitrene equivalents for a highly chemoselective and regioselective addition across electron-rich C[BOND]C triple bonds.

    24. Homogeneous Catalysis

      Rearrangement of 2-Aryloxybenzaldehydes to 2-Hydroxybenzophenones by Rhodium-Catalyzed Cleavage of Aryloxy C[BOND]O Bonds (pages 8936–8939)

      Dr. Honghua Rao and Prof. Dr. Chao-Jun Li

      Article first published online: 10 AUG 2011 | DOI: 10.1002/anie.201103599

      Thumbnail image of graphical abstract

      Lost in the shuffle: An unprecedented rearrangement of the title compounds proceeds by the simultaneous rhodium-catalyzed cleavage of aryloxy C[BOND]O and aldehyde C[BOND]H bonds (see scheme). The reaction tolerates the presence of various catalytically reactive substituents such as aryl halides, nitrile, and esters.

    25. Spin Crossover

      Spin-Crossover FeII4 Squares: Two-Step Complete Spin Transition and Reversible Single-Crystal-to-Single-Crystal Transformation (pages 8940–8943)

      Rong-Jia Wei, Qian Huo, Prof. Jun Tao, Prof. Rong-Bin Huang and Prof. Lan-Sun Zheng

      Article first published online: 2 AUG 2011 | DOI: 10.1002/anie.201103648

      Thumbnail image of graphical abstract

      High or low? A square FeII4 compound exhibits complete thermally and optically activated transition from four low-spin (LS) centers to four high-spin (HS) centers in two steps (see plot of magnetic susceptibility). Reversible desorption and resorption of guest water molecules causes a single-crystal-to-single-crystal transformation.

    26. Synthetic Methods

      Highly N2-Selective Palladium-Catalyzed Arylation of 1,2,3-Triazoles (pages 8944–8947)

      Dr. Satoshi Ueda, Mingjuan Su and Prof. Dr. Stephen L. Buchwald

      Article first published online: 18 AUG 2011 | DOI: 10.1002/anie.201103882

      Thumbnail image of graphical abstract

      A familiar ring? Highly N2-selective arylation of 4,5-unsubstituted and 4-substituted 1,2,3-triazoles was achieved for the first time by the Pd/1 catalyst system. A wide range of N2-aryl-1,2,3-triazoles were prepared from aryl bromides, chlorides, and triflates with excellent N2 selectivity (see scheme). Density functional theory calculations suggest that the formation of N2-arylated 1,2,3-triazoles is favored kinetically. dba=dibenzylideneacetone, Tf=trifluoromethanesulfonyl.

    27. Multicomponent Reactions

      Palladium-Catalyzed Aryl Iodide Carbonylation as a Route to Imidazoline Synthesis: Design of a Five-Component Coupling Reaction (pages 8948–8951)

      Dr. Sébastien Bontemps, Jeffrey S. Quesnel, Kraig Worrall and Prof. Bruce A. Arndtsen

      Article first published online: 17 AUG 2011 | DOI: 10.1002/anie.201103885

      Thumbnail image of graphical abstract

      Take five: A new method employing aryl halide carbonylation to directly access heterocycles has been described (see scheme). In a single palladium-catalyzed reaction the catalyst mediates two consecutive carbonylation steps, thereby converting five components (aryl iodide, two units imine, and two units CO) into an imidazoline ring.

    28. Asymmetric Catalysis

      Catalytic Asymmetric Alkynylation of C1-Substituted C,N-Cyclic Azomethine Imines by CuI/Chiral Brønsted Acid Co-Catalyst (pages 8952–8955)

      Dr. Takuya Hashimoto, Masato Omote and Prof. Dr. Keiji Maruoka

      Article first published online: 10 AUG 2011 | DOI: 10.1002/anie.201104017

      Thumbnail image of graphical abstract

      It all adds up: The title reaction was developed for the synthesis of chiral tetrahydroisoquinoline derivatives with a tetrasubstituted carbon center at the C1-position (see scheme, Bz=benzoyl, pybox=2,6-bis(2-oxazolinyl)pyridine). The reaction was facilitated effectively by the co-catalyst system composed of copper(I)/Ph-pybox and an axially chiral dicarboxylic acid.

    29. Cycloaddition

      Nickel-Catalyzed Cycloaddition of α,β,γ,δ-Unsaturated Ketones with Alkynes (pages 8956–8959)

      Hiroaki Horie, Dr. Takuya Kurahashi and Prof. Dr. Seijiro Matsubara

      Article first published online: 19 AUG 2011 | DOI: 10.1002/anie.201104286

      Thumbnail image of graphical abstract

      As easy as α, β, γ, δ: The title reaction unexpectedly resulted in the stereoselective synthesis of bicyclo[3.1.0]hexenes (see scheme). The high level of stereoselection is attributed to a mechanistic pathway involving the oxidative cyclization of nickel(0) with α,β,γ,δ-unsaturated ketones and alkynes, and the subsequent intramolecular carbonickelation.

    30. Energetic Materials

      Improved Stability and Smart-Material Functionality Realized in an Energetic Cocrystal (pages 8960–8963)

      Dr. Onas Bolton and Prof. Adam J. Matzger

      Article first published online: 25 AUG 2011 | DOI: 10.1002/anie.201104164

      Thumbnail image of graphical abstract

      Handle with care: CL-20, a high-power explosive suffering from high sensitivity, has been cocrystallized with TNT to produce a novel high-power, low-sensitivity explosive. This cocrystal can be used directly for explosives applications or stored in this insensitive form then activated by heat to return it to its high-sensitivity form.

    31. Sustainable Chemistry

      Depolymerization of Cellulose Assisted by a Nonthermal Atmospheric Plasma (pages 8964–8967)

      Maud Benoit, Anthony Rodrigues, Dr. Qinghua Zhang, Dr. Elodie Fourré, Dr. Karine De Oliveira Vigier, Dr. Jean-Michel Tatibouët and Dr. François Jérôme

      Article first published online: 19 AUG 2011 | DOI: 10.1002/anie.201104123

      Thumbnail image of graphical abstract

      Biomass breakdown: The reactivity of recalcitrant cellulose towards hydrolysis is enhanced by pretreatment with a nonthermal atmospheric plasma. Glucose was produced in up to 25 wt % yield from microcrystalline cellulose and α-cellulose (see picture). This technology is also applicable to the deconstruction of starch and inulin.

    32. Synthetic Methods

      Copper-Catalyzed Intramolecular Oxidative 6-exo-trig Cyclization of 1,6-Enynes with H2O and O2 (pages 8968–8973)

      Zhi-Qiang Wang, Wen-Wu Zhang, Lu-Bin Gong, Ri-Yuan Tang, Xu-Heng Yang, Yu Liu and Prof. Dr. Jin-Heng Li

      Article first published online: 19 AUG 2011 | DOI: 10.1002/anie.201104082

      Thumbnail image of graphical abstract

      The novel CuCl2-catalyzed title reaction of enynes has been developed for synthesizing substituted naphthoquinones (see scheme; DMA=dimethylacetamide). The method represents the first example of a copper-catalyzed enyne oxidative cyclization for constructing 1,4-naphthoquinones by the incorporation of two oxygen atoms into the organic framework from molecular oxygen and water.

    33. P,N Biradicaloids

      [P(μ-NTer)]2: A Biradicaloid That Is Stable at High Temperature (pages 8974–8978)

      Dr. Torsten Beweries, Rene Kuzora, Prof. Dr. Uwe Rosenthal, Prof. Dr. Axel Schulz and Dr. Alexander Villinger

      Article first published online: 19 AUG 2011 | DOI: 10.1002/anie.201103742

      Thumbnail image of graphical abstract

      Radical protection makes a biradical: High-temperature-stable biradicaloids [P(μ-NR)]2 (R=Ter, Hyp) were isolated from [ClP(μ-NR)]2 when mild reducing agents were employed. The bulky substituents prevent dimerization. Ter=2,6-Mes2C6H3, with Mes=2,4,6-Me3C6H2; Hyp=(Me3Si)3Si.

    34. Asymmetric Transfer Hydrogenation

      Iridium Diamine Catalyst for the Asymmetric Transfer Hydrogenation of Ketones (pages 8979–8981)

      Dr. Henar Vázquez-Villa, Dr. Stefan Reber, Martin A. Ariger and Prof. Dr. Erick M. Carreira

      Article first published online: 25 AUG 2011 | DOI: 10.1002/anie.201102732

      Thumbnail image of graphical abstract

      A simple and very efficient chiral aqua iridium(III) diamine complex leads to excellent enantioselectivities in the asymmetric transfer hydrogenation of various α-cyano and α-nitro ketones. The catalyst provides the ortho-substituted aromatic alcohols with especially high ee values. The diamine ligands can be used directly as chiral ligands; conversion into the corresponding sulfamide is not necessary.

    35. Phosphorus Ligands

      Access to Phosphorus-Rich Zirconium Complexes (pages 8982–8985)

      Dr. Ulf Vogel, Dr. Miriam Eberl, Maria Eckhardt, Andreas Seitz, Eva-Maria Rummel, Dr. Alexey Y. Timoshkin, Dr. Eugenia V. Peresypkina and Prof. Dr. Manfred Scheer

      Article first published online: 24 AUG 2011 | DOI: 10.1002/anie.201103634

      Thumbnail image of graphical abstract

      The missing member [Cp′′2Zr(η2-P3CtBu)] (Cp′′=η5-C5H3tBu2) of the phosphorus-containing bicyclobutane zirconium complex family was synthesized by reaction between tetraphosphazirconocene derivative [Cp′′2Zr(η2-P4)] and a phosphaalkyne with the release of a formal P2 unit. Synthetic evidence of another unknown isomer [Cp′′2Zr(η2-P2(CtBu)2)] was found; according to DFT calculations, it is the stable form if a Cp′′2Zr moiety is used.

    36. Transfection Polymers

      Solid-Phase Synthesis of Sequence-Defined T-, i-, and U-Shape Polymers for pDNA and siRNA Delivery (pages 8986–8989)

      Dr. David Schaffert, Christina Troiber, Eveline E. Salcher, Thomas Fröhlich, Irene Martin, Dr. Naresh Badgujar, Christian Dohmen, Daniel Edinger, Raphaela Kläger, Dr. Gelja Maiwald, Katarina Farkasova, Dr. Silke Seeber, Dr. Kerstin Jahn-Hofmann, Dr. Philipp Hadwiger and Prof. Ernst Wagner

      Article first published online: 11 AUG 2011 | DOI: 10.1002/anie.201102165

      Thumbnail image of graphical abstract

      Artificial oligo(ethylene amino) acids, together with selected natural amino acids and fatty acid modifications, have been used for the solid-phase-assisted synthesis of polymers with precise sequence, topology, and modifications (see picture). First proof-of-concept studies demonstrate the high potential of such polymers in pDNA and siRNA delivery. K=lysine, A=alanine.

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      Preview: Angew. Chem. Int. Ed. 39/2011 (page 8991)

      Article first published online: 8 SEP 2011 | DOI: 10.1002/anie.201190079

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