Angewandte Chemie International Edition

Cover image for Vol. 51 Issue 32

August 6, 2012

Volume 51, Issue 32

Pages 7863–8117

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. You have free access to this content
      Cover Picture: Enantioselective Total Synthesis of Amphidinolide F (Angew. Chem. Int. Ed. 32/2012) (page 7863)

      Subham Mahapatra and Prof. Dr. Rich G. Carter

      Article first published online: 18 JUL 2012 | DOI: 10.1002/anie.201205172

      Thumbnail image of graphical abstract

      Hidden symmetry within the THF-containing moieties of the macrocycle of amphidinolide F led S. Mahapatra and R. G. Carter to employ a synthetic strategy including a common intermediate, as reported in their Communication on page 7948 ff. The cover picture highlights key steps of the total synthesis as well as the locations on both sides of the Pacific of the initial characterization (Hokkaido University) and first synthesis (Oregon State University) of the natural product.

    2. You have free access to this content
      Inside Cover: Polyspermine Imidazole-4,5-imine, a Chemically Dynamic and Biologically Responsive Carrier System for Intracellular Delivery of siRNA (Angew. Chem. Int. Ed. 32/2012) (page 7864)

      Shiyue Duan, Weien Yuan, Fei Wu and Tuo Jin

      Article first published online: 23 JUL 2012 | DOI: 10.1002/anie.201205175

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      Unlocking the endosome allows the release of siRNAs into the cytoplasm following the cellular uptake of nanoparticles made up of siRNAs and polyspermine imidazole-4,5-imine. In their Communication on page 7938 ff., T. Jin and co-workers show that a polymer of spermine with a pH-sensitive linkage degrades, upon entry into the endosome, into spermine and a nontoxic metabolite. Assays in cells and mice showed effective gene silencing by the polymer-packaged siRNAs without cytotoxicity.

    3. You have free access to this content
      Inside Back Cover: Microfluidic Control of the Internal Morphology in Nanofiber-Based Macroscopic Cables (Angew. Chem. Int. Ed. 32/2012) (page 8121)

      Dr. Daisuke Kiriya, Dr. Ryuji Kawano, Dr. Hiroaki Onoe and Prof. Dr. Shoji Takeuchi

      Article first published online: 23 JUL 2012 | DOI: 10.1002/anie.201205503

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      Macroscopic cables that consist of assembled nanofibers are described by S. Takeuchi and co-workers in their Communication on page 7942 ff. The nanofibers in the cables can be oriented parallel or perpendicular to the longitudinal axis by regulating the fluidic velocities of the core and sheath flows in coaxial microfluidic devices. These cables with controlled internal morphology exhibit a difference in their electrical conductivity and mechanical properties depending on their morphology.

    4. You have free access to this content
      Back Cover: Unconventional Chain-Growth Mode in the Assembly of Colloidal Gold Nanoparticles (Angew. Chem. Int. Ed. 32/2012) (page 8122)

      Hong Wang, Liyong Chen, Xiaoshuang Shen, Liangfang Zhu, Jiating He and Prof. Hongyu Chen

      Article first published online: 18 JUL 2012 | DOI: 10.1002/anie.201205216

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      The “chain-growth polymerization” of gold nanoparticles involves their initial encapsulation by polystyrene-block-poly(acrylic acid) and the self-assembly of the resulting “monomers” into long chains of up to 300 nanoparticles. In their Communication on page 8021 ff., H. Chen et al. state that the nanoparticle assembly is highly selective and gives chains with uniform width and interparticle spacing. The background of the picture shows the skyline of Singapore.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 32/2012 (pages 7867–7882)

      Article first published online: 1 AUG 2012 | DOI: 10.1002/anie.201290060

  3. Corrigenda

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. You have free access to this content
      Corrigendum: Synthesis and Microcontact Printing of Dual End-Functionalized Mucin-like Glycopolymers for Microarray Applications (page 7881)

      Kamil Godula, David Rabuka, Ki Tae Nam and Carolyn R. Bertozzi

      Article first published online: 1 AUG 2012 | DOI: 10.1002/anie.201204575

      This article corrects:
    2. You have free access to this content
      Corrigendum: Oxygen-Independent Decarbonylation of Aldehydes by Cyanobacterial Aldehyde Decarbonylase: A New Reaction of Diiron Enzymes (page 7881)

      Debasis Das, Dr. Bekir E. Eser, Prof. Jaehong Han, Aaron Sciore and Prof. E. Neil G. Marsh

      Article first published online: 1 AUG 2012 | DOI: 10.1002/anie.201204831

      This article corrects:
    3. You have free access to this content
      Corrigendum: Low-Temperature Isolation of An Azidophosphenium Cation (page 7882)

      Christian Hering, Prof. Dr. Axel Schulz and Dr. Alexander Villinger

      Article first published online: 1 AUG 2012 | DOI: 10.1002/anie.201205222

      This article corrects:

      Low-Temperature Isolation of An Azidophosphenium Cation1

      Vol. 51, Issue 25, 6241–6245, Article first published online: 4 MAY 2012

  4. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Stephen B. H. Kent (page 7888)

      Article first published online: 8 MAY 2012 | DOI: 10.1002/anie.201201191

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      “My favorite piece of music is La Bohème (Puccini). My best investment was in the university education of our three children. …” This and more about Stephen B. H. Kent can be found on page 7888.

  6. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Corrigenda
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Organic Syntheses Based on Name Reactions. A Practical Guide to 750 Transformations. 3rd Edition. By Alfred Hassner and Irishi Namboothiri. (page 7890)

      Ulrich Hennecke

      Article first published online: 29 JUN 2012 | DOI: 10.1002/anie.201203537

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      Elsevier, Amsterdam, 2011. 612 pp., hardcover, € 57.95.—ISBN 978-0080966304

  8. Highlights

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

      Molecular Organic Crystals: From Barely Porous to Really Porous (pages 7892–7894)

      Prof. Andrew I. Cooper

      Article first published online: 27 JUN 2012 | DOI: 10.1002/anie.201203117

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      Holey suitable crystals: A trisbenzimidazolone molecule self-assembles by hydrogen bonding to form a permanently porous crystal with an apparent surface area, SABET, of 2796 m2 g−1 (see scheme), demonstrating that extrinsic, intermolecular porosity is a viable strategy for highly porous materials.

    2. Photopolymerizations

      Novel Synthetic Pathways for Bis(acyl)phosphine Oxide Photoinitiators (pages 7895–7897)

      Dr. Luca Gonsalvi and Dr. Maurizio Peruzzini

      Article first published online: 4 JUL 2012 | DOI: 10.1002/anie.201203648

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      Photoactive: A cheap, safe, and widely functional-group-tolerant synthetic protocol to an important class of photoinitiators, bis(acyl)phosphine oxides (BAPOs), has been disclosed, together with examples of application to stain-proof fabrics and photoactive polymeric films.

  9. Review

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

      Functional Block Copolymers: Nanostructured Materials with Emerging Applications (pages 7898–7921)

      Jun.-Prof. Dr. Felix H. Schacher, Dr. Paul A. Rupar and Prof. Ian Manners

      Article first published online: 16 JUL 2012 | DOI: 10.1002/anie.201200310

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      Form and function: Functional block copolymers of well-defined composition and length are readily available today thanks to recent advances in synthetic polymer chemistry. Their ability to self-assemble into a great diversity of structures on the nanoscale, along with their customizable chemical functionalities, makes block copolymers highly desirable materials for a wide range of applications.

  10. Communications

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

      Rewiring Chemistry: Algorithmic Discovery and Experimental Validation of One-Pot Reactions in the Network of Organic Chemistry (pages 7922–7927)

      Dr. Chris M. Gothard, Dr. Siowling Soh, Nosheen A. Gothard, Dr. Bartlomiej Kowalczyk, Dr. Yanhu Wei, Dr. Bilge Baytekin and Prof. Bartosz A. Grzybowski

      Article first published online: 13 JUL 2012 | DOI: 10.1002/anie.201202155

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      Computational algorithms are used to identify sequences of reactions that can be performed in one pot. These predictions are based on over 86 000 chemical criteria by which the putative sequences are evaluated. The “raw” algorithmic output is then validated experimentally by performing multiple two-, three-, and even four-step sequences. These sequences “rewire” synthetic pathways around popular and/or important small molecules.

    2. Chemical Networks (2)

      Parallel Optimization of Synthetic Pathways within the Network of Organic Chemistry (pages 7928–7932)

      Dr. Mikołaj Kowalik, Dr. Chris M. Gothard, Aaron M. Drews, Nosheen A. Gothard, Alex Weckiewicz, Patrick E. Fuller, Prof. Bartosz A. Grzybowski and Prof. Kyle J. M. Bishop

      Article first published online: 13 JUL 2012 | DOI: 10.1002/anie.201202209

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      Finding a needle in a haystack: The number of possible synthetic pathways leading to the desired target of a synthesis can be astronomical (1019 within five synthetic steps). Algorithms are described that navigate through the entire known chemical-synthetic knowledge to identify optimal synthetic pathways. Examples are provided to illustrate single-target optimization and parallel optimization of syntheses leading to multiple targets.

    3. Chemical Networks (3)

      Chemical Network Algorithms for the Risk Assessment and Management of Chemical Threats (pages 7933–7937)

      Patrick E. Fuller, Dr. Chris M. Gothard, Nosheen A. Gothard, Alex Weckiewicz and Prof. Bartosz A. Grzybowski

      Article first published online: 13 JUL 2012 | DOI: 10.1002/anie.201202210

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      A network of chemical threats: Current regulatory protocols are insufficient to monitor and block many short-route syntheses of chemical weapons, including those that start from household products. Network searches combined with game-theory algorithms provide an effective means of identifying and eliminating chemical threats. (Picture: an algorithm-detected pathway that yields sarin (bright red node) in three steps from unregulated substances.)

    4. siRNA Delivery

      Polyspermine Imidazole-4,5-imine, a Chemically Dynamic and Biologically Responsive Carrier System for Intracellular Delivery of siRNA (pages 7938–7941)

      Shiyue Duan, Weien Yuan, Fei Wu and Tuo Jin

      Article first published online: 16 JUL 2012 | DOI: 10.1002/anie.201201793

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      Silence please! Polyspermine imidazole-4,5-imine (blue lines) was formed by condensing spermine with bisformaldehyde imidazole through a pH-responsive linkage. This polymer was used to condense siRNAs into nanoparticles (see scheme) and studied for delivery into cells and release from endosomes. Cellular and in vivo assays indicated that this siRNA carrier was efficient in silencing target genes with negligible cytotoxicity.

    5. Materials Science

      Microfluidic Control of the Internal Morphology in Nanofiber-Based Macroscopic Cables (pages 7942–7947)

      Dr. Daisuke Kiriya, Dr. Ryuji Kawano, Dr. Hiroaki Onoe and Prof. Dr. Shoji Takeuchi

      Article first published online: 23 JUL 2012 | DOI: 10.1002/anie.201202078

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      A matter of orientation: The nanofibers in cables that consist of assemblies of these nanofibers can be oriented parallel or perpendicular to the longitudinal axis by regulating the fluidic velocities of the core and sheath flows in coaxial microfluidic devices (see picture). Control of the internal morphology enables fabrication of cables with improved electrical conductivity and mechanical properties.

    6. Hidden Symmetry

      Enantioselective Total Synthesis of Amphidinolide F (pages 7948–7951)

      Subham Mahapatra and Prof. Dr. Rich G. Carter

      Article first published online: 5 JUL 2012 | DOI: 10.1002/anie.201203935

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      A common-intermediate approach is utilized in the total synthesis of amphidinolide F (see scheme, left) to access both the C1–C8 and the C18–C25 portions of the macrolide. A silver-catalyzed rearrangement/cyclization was employed to construct the two tetrahydrofuran rings. A Felkin-controlled, dienyl lithium addition to an α-chiral aldehyde incorporated both the C9–C11 diene and the alcohol at C8. An umpolung sulfone alkylation/oxidative desulfurization sequence is employed to couple the two moieties.

    7. DNA Pentaplex Structure

      Solution Structure of a Parallel-Stranded Oligoisoguanine DNA Pentaplex Formed by d(T(iG)4T) in the Presence of Cs+ Ions (pages 7952–7955)

      Dr. Mijeong Kang, Dr. Ben Heuberger, Dr. John C. Chaput, Prof. Dr. Christopher Switzer and Prof. Dr. Juli Feigon

      Article first published online: 5 JUL 2012 | DOI: 10.1002/anie.201203459

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      What a pentaplexing situation: Isoguanine (iG) is an isomer of guanine, where the positions of the C2 amino group and the C6 carboxy group are swapped. iG can self-assemble into pentads in the presence of alkali metal cations. Cs+ ions were found to stabilize a pentaplex of d(T(iG)4T). Solution NMR studies of this pentaplex in the presence of Cs+ ions (or Na+, K+, Rb+, or NH4+ cations) demonstrate its stability and structure (see picture).

    8. Heterogeneous Catalysis

      Watching the Methanol-to-Olefin Process with Time- and Space-Resolved High-Energy Operando X-ray Diffraction (pages 7956–7959)

      Dr. David S. Wragg, Dr. Matthew G. O'Brien, Dr. Francesca L. Bleken, Dr. Marco Di Michiel, Prof. Unni Olsbye and Prof. Helmer Fjellvåg

      Article first published online: 2 JUL 2012 | DOI: 10.1002/anie.201203462

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      The movement of reactants in a large methanol-to-olefin reactor bed was visualized by fast scanning synchrotron X-ray diffraction (see picture). Changes in the structure of the catalyst showed the formation of reaction intermediates and coke, which can be tracked along the reactor bed. The observations lead to a new model for the progress of the reaction and explain the role of methanol in coke formation.

    9. Laser Chemistry

      Single-Ion Recycling Reactions (pages 7960–7962)

      Anders K. Hansen, Magnus A. Sørensen, Dr. Peter F. Staanum and Prof. Dr. Michael Drewsen

      Article first published online: 5 JUL 2012 | DOI: 10.1002/anie.201203550

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      A single ion is enough: Ion reaction rates and reaction product branching ratios could be determined through repeated regeneration of the original target ion by photodissociation after each reaction. The product molecule was identified through nondestructive mass spectrometry. Finally, the target ion was regenerated through photodissociation of the molecular ion (see picture).

    10. Solid-State NMR Spectroscopy

      A Native-Like Conformation for the C-Terminal Domain of the Prion Ure2p within its Fibrillar Form (pages 7963–7966)

      Dr. Birgit Habenstein, Dr. Luc Bousset, Yannick Sourigues, Dr. Mehdi Kabani, Dr. Antoine Loquet, Prof. Dr. Beat H. Meier, Dr. Ronald Melki and Dr. Anja Böckmann

      Article first published online: 3 JUL 2012 | DOI: 10.1002/anie.201202093

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      Taking a definite stance: Protein fibrils are often associated with disorder and polymorphism, but the prion fibrils of Ure2p are shown (through solid-state NMR spectroscopy) to be highly ordered, and the conformations of the globular domain to be more restricted within the fibrils (black; see scheme) than in Ure2p single crystals (red). This finding implies that steric impairment is at the origin of the [URE3] phenotype in yeast.

    11. Supramolecular Chemistry

      Asymmetric Induction in the Preparation of Helical Receptor–Anion Complexes: Ion-Pair Formation with Chiral Cations (pages 7967–7971)

      Dr. Yohei Haketa, Yuya Bando, Dr. Kazuto Takaishi, Prof. Dr. Masanobu Uchiyama, Dr. Atsuya Muranaka, Prof. Dr. Masanobu Naito, Hiroshi Shibaguchi, Prof. Dr. Tsuyoshi Kawai and Prof. Dr. Hiromitsu Maeda

      Article first published online: 28 JUN 2012 | DOI: 10.1002/anie.201202196

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      Asymmetry through ion pairing: Upon addition of chloride and bromide ions, as chiral ammonium salts, to solutions of pyrrole-based π-conjugated linear oligomers, helical structures form with asymmetric induction, which is guided by the formation of diastereomeric ion pairs with chiral counter cations (see picture). These ions pairs exhibit circular dichroism (CD) and strong circularly polarized luminescence (CPL) with glum values of greater than 0.1.

    12. Single-Molecule Chemistry

      S-Nitrosothiol Chemistry at the Single-Molecule Level (pages 7972–7976)

      Lai-Sheung Choi and Hagan Bayley

      Article first published online: 4 JUL 2012 | DOI: 10.1002/anie.201202365

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      SNO patrol: S-Nitrosothiols (RSNO) are important molecules involved in cell signaling, which control physiological processes such as vasodilation and bronchodilation. By using the protein pore α-hemolysin as a nanoreactor, the biological chemistry of RSNO has been investigated at the single-molecule level (see scheme).

    13. Piezoceramics

      Polarization Rotation in the Monoclinic Perovskite BiCo1−xFexO3 (pages 7977–7980)

      Dr. Kengo Oka, Tsukasa Koyama, Tomoatsu Ozaaki, Prof. Dr. Shigeo Mori, Prof. Dr. Yuichi Shimakawa and Prof. Dr. Masaki Azuma

      Article first published online: 2 JUL 2012 | DOI: 10.1002/anie.201202644

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      The monoclinic perovskite BiCo1−xFexO3 (x≈0.7) undergoes a second-order structural transition from tetragonal to monoclinic, which is accompanied by a rotation of the polarization vector from the [001] to [111] directions of a pseudo cubic cell. The crystal structure, determined by electron diffraction and powder synchrotron X-ray diffraction, was the same as that of Pb(Ti1−xZrx)O3 at the morphotropic phase boundary.

      Corrected by:

      Corrigendum: Corrigendum: Polarization Rotation in the Monoclinic Perovskite BiCo1−xFexO3

      Vol. 51, Issue 42, 10436, Article first published online: 10 OCT 2012

    14. Interfacial Catalysis

      Investigation of “On Water” Conditions Using a Biphasic Fluidic Platform (pages 7981–7984)

      Sonia Mellouli, Lise Bousekkine, Dr. Ashleigh B. Theberge and Prof. Dr. Wilhelm T. S. Huck

      Article first published online: 2 JUL 2012 | DOI: 10.1002/anie.201200575

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      Converting the DEAD: A fluidic approach to generate precisely defined water–oil interfaces (see scheme) was used to quantify the influence of the water surface (blue drops) on chemical reactions between quadricyclane or β-pinene and diethyl azodicarboxylate (DEAD). This method allows for easy investigation of the “on water” effect.

    15. Polyoxometalates

      An Ionothermal Synthetic Approach to Porous Polyoxometalate-Based Metal–Organic Frameworks (pages 7985–7989)

      Dr. Hai Fu, Prof. Chao Qin, Prof. Ying Lu, Dr. Zhi-Ming Zhang, Prof. Yang-Guang Li, Prof. Zhong-Min Su, Dr. Wen-Liang Li and Prof. En-Bo Wang

      Article first published online: 2 JUL 2012 | DOI: 10.1002/anie.201202994

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      Pretty porous POMs: Ionothermal synthesis was applied to prepare porous POM-based open frameworks. The structural integrity remains unchanged until 300 °C; most importantly, the bulky tetrabutylammonium cations within their nanosized channels can be replaced by transition-metal ions through a cation-exchange process, and subsequent gas adsorption measurements confirm their permanent porosity.

    16. Liquid Crystals

      Wide-Range 2D Lattice Correlation Unveiled for Columnarly Assembled Triphenylene Hexacarboxylic Esters (pages 7990–7993)

      Dr. Terutsune Osawa, Dr. Takashi Kajitani, Dr. Daisuke Hashizume, Dr. Hiroyuki Ohsumi, Dr. Sono Sasaki, Prof. Dr. Masaki Takata, Dr. Yoshiko Koizumi, Dr. Akinori Saeki, Prof. Dr. Shu Seki, Prof. Dr. Takanori Fukushima and Prof. Dr. Takuzo Aida

      Article first published online: 29 JUN 2012 | DOI: 10.1002/anie.201203077

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      Dipole bridge: Liquid-crystalline (LC) triphenylenes (see picture) self-assemble columnarly into a hexagonal geometry with a wide-range 2D lattice correlation, for which distal and proximal dipole–dipole interactions are considered responsible. By virtue of the strong intercolumnar interaction, the LC columns of the triphenylene can spontaneously align homeotropically on the 12 different substrates examined (POM=polarized optical microscopy).

    17. Boron Macrocycles

      π-Expanded Borazine: An Ambipolar Conjugated B–π–N Macrocycle (pages 7994–7998)

      Pangkuan Chen, Prof. Dr. Roger A. Lalancette and Prof. Dr. Frieder Jäkle

      Article first published online: 5 JUL 2012 | DOI: 10.1002/anie.201203788

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      Staying at a B ′N′ B: A highly symmetric cyclic structure in which N donor and B acceptor sites are alternating (see picture) is found for the first ambipolar π-conjugated B–N macrocycle. The donor–π–acceptor arrangement results in mutual interactions between B and N and a pronounced solvatochromic effect on the emission. The strong luminescence in solution also lends itself to use in anion recognition.

    18. DNA Self-Assembly

      Controlling the Chirality of DNA Nanocages (pages 7999–8002)

      Chuan Zhang, Weimin Wu, Xiang Li, Cheng Tian, Hang Qian, Guansong Wang, Wen Jiang and Chengde Mao

      Article first published online: 3 JUL 2012 | DOI: 10.1002/anie.201203875

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      Playing DNA Twister: By using asymmetric DNA building blocks, self-assembled DNA nanocages that are chiral on the nanoscale have been designed. The resulting DNA nanocages have been characterized with a variety of methods. Such chiral control could be useful for tuning the photonic/optical properties of DNA-templated nanostructures.

    19. Multibond-Breaking Reactions

      A One-Step Four-Bond-Breaking Reaction Catalyzed by an Electron (pages 8003–8007)

      Dr. Daly Davis, Victor P. Vysotskiy, Dr. Y. Sajeev and Prof. Dr. Lorenz S. Cederbaum

      Article first published online: 5 JUL 2012 | DOI: 10.1002/anie.201204162

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      Molecular demolition: Long-lived compound states involving a low-energy electron and a molecule generally involve the breaking of only one σ bond in the first elementary reaction step. Using high-level ab initio quantum-chemical methods, four-bond breaking in an elementary reaction step has been identified. Upon electron impact, a bicyclic molecule is shown to break four σ bonds in a concerted and essentially barrierless reaction step, producing three closed-shell neutral molecules.

    20. Carbon Sequestration

      Photocatalytic Conversion of CO2 in Water over Layered Double Hydroxides (pages 8008–8011)

      Dr. Kentaro Teramura, Shoji Iguchi, Yuto Mizuno, Prof. Dr. Tetsuya Shishido and Prof. Dr. Tsunehiro Tanaka

      Article first published online: 3 JUL 2012 | DOI: 10.1002/anie.201201847

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      Have a bit of bubbly: Significant amounts of CO and O2 gas are evolved in the photocatalytic conversion of CO2 over layered double hydroxides (LDHs) in water (see scheme). A simple mixture of the same metal hydroxides, which has the same constituent elements of the LDH, shows low activity for CO and O2 evolution. Dissolved CO2 gas was shown to be the source of carbon in the reaction over LDHs in water.

    21. Heterocycles

      Catalyst-Free N-Arylation Using Unactivated Fluorobenzenes (pages 8012–8016)

      Dr. Frederik Diness and Prof. David P. Fairlie

      Article first published online: 2 JUL 2012 | DOI: 10.1002/anie.201202149

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      Caught in a ‘SNAr'e: A one-step, high-yielding, catalyst-free method is described for N-arylation of azoles and indoles from unactivated monofluorobenzenes. This SNAr reaction tolerates a wide range of substituents and can also generate halogenated N-aryl products. The reaction can also be performed simultaneously with or subsequent to a copper- or palladium-catalyzed cross-coupling reaction in the same pot.

    22. Heterogeneous Catalysis

      Heterogeneous Synergistic Catalysis by a Palladium Complex and an Amine on a Silica Surface for Acceleration of the Tsuji–Trost Reaction (pages 8017–8020)

      Hiroto Noda, Dr. Ken Motokura, Dr. Akimitsu Miyaji and Prof. Dr. Toshihide Baba

      Article first published online: 5 JUL 2012 | DOI: 10.1002/anie.201203066

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      The cooperative surface-catalysis strategy of a Brønsted acid and an organic base can be extended to a metal complex and organic base pair. A silica-supported diaminopalladium complex and a tertiary amine were prepared and characterized. The Pd-catalyzed Tsuji–Trost reaction was enhanced significantly by the presence of the tertiary amine on the same silica surface as the Pd complex.

    23. Nanoparticle Chains

      Unconventional Chain-Growth Mode in the Assembly of Colloidal Gold Nanoparticles (pages 8021–8025)

      Hong Wang, Liyong Chen, Xiaoshuang Shen, Liangfang Zhu, Jiating He and Prof. Hongyu Chen

      Article first published online: 18 JUL 2012 | DOI: 10.1002/anie.201203088

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      One-dimensional assembly of gold nanoparticles (see picture)is achieved by a sphere-to-cylinder transformation of polymer shells. A large amount of monomers remains after the assembly, which is characteristic of the chain-growth “polymerization”. Single-line chains can be converted to double-line chains, thus substantiating the unique role of the polymer shell.

    24. Natural Product Synthesis

      Total Synthesis of (+)-Davidiin (pages 8026–8029)

      Dr. Yusuke Kasai, Naoki Michihata, Hidehisa Nishimura, Tsukasa Hirokane and Prof. Dr. Hidetoshi Yamada

      Article first published online: 2 JUL 2012 | DOI: 10.1002/anie.201203305

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      Quite strained: The total synthesis of (+)-davidiin, an ellagitannin with more substituents in axial than in equatorial positions, requires a conformational lock of the glucose, induced by steric repulsion between adjacent bulky silyloxy groups. This conformational lock played a pivotal role in 1) the β-selective formation of the glycosyl ester at the anomeric position, 2) the formation of the 1,6-HHDP bridge, and 3) the complete control of axial chirality in the aryl–aryl coupling.

    25. Organometallic Complexes

      A Simple Approach to Room Temperature Phosphorescent Allenylidene Complexes (pages 8030–8033)

      Dr. Florian Kessler, Basile F. E. Curchod, Dr. Ivano Tavernelli, Prof. Ursula Rothlisberger, Dr. Rosario Scopelliti, Dr. Davide Di Censo, Prof. Michael Grätzel, Dr. Md. Khaja Nazeeruddin and Dr. Etienne Baranoff

      Article first published online: 29 JUN 2012 | DOI: 10.1002/anie.201203329

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      A warm (blue) glow: A stable bis-cyclometalated iridium(III) allenylidene complex is prepared from a bis-cyclometalated iridium(III) complex (see scheme). This strategy gives the first allenylidene complex that is phosphorescent at room temperature.

    26. Nanostructures

      Diffusion through the Shells of Yolk–Shell and Core–Shell Nanostructures in the Liquid Phase (pages 8034–8036)

      Xiaoliang Liang, Jie Li, Dr. Ji Bong Joo, Dr. Alejandro Gutiérrez, Dr. Aashani Tillekaratne, Dr. Ilkeun Lee, Prof. Yadong Yin and Prof. Francisco Zaera

      Article first published online: 29 JUN 2012 | DOI: 10.1002/anie.201203456

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      Easy in, easy out: Mass transport through TiO2 and SiO2 shells was probed in the liquid phase with IR spectroscopy by detecting carbon monoxide adsorption in Pt@void@TiO2 yolk–shell and Pt@SiO2 core–shell nanostructures (see picture; C green, O red, Pt pale red). Adsorption was observed on the surface of Pt nanoparticle cores, and on the inner face of the TiO2 shells in the yolk–shell case.

    27. Synthetic Methods

      Ugi/Aldol Sequence: Expeditious Entry to Several Families of Densely Substituted Nitrogen Heterocycles (pages 8037–8040)

      Zhigang Xu, Fabio De Moliner, Alexandra P. Cappelli and Christopher Hulme

      Article first published online: 29 JUN 2012 | DOI: 10.1002/anie.201202575

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      Complexity from simplicity: Nitrogen-containing heterocycles have been assembled by means of unprecedented domino processes designed to take advantage of diversity assembly using strategically decorated Ugi products (see scheme). The aldol reaction is the second common denominator which enables sequences of up to five steps in one pot, thus producing unique molecular architectures in rapid fashion.

    28. Asymmetric Syntheses of 8-Oxabicyclo[3,2,1]octanes: A Cationic Cascade Cyclization (pages 8041–8045)

      Bin Li, Dr. Yu-Jun Zhao, Yin-Chang Lai and Prof. Teck-Peng Loh

      Article first published online: 2 JUL 2012 | DOI: 10.1002/anie.201202699

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      High octane: A novel and practical syntheses of 8-oxabicyclo[3.2.1]octanes using a cationic cascade cyclization reaction has been developed (see scheme; TIPS=triisopropylsilyl). The diastereomer of the cyclization product isolated depends upon whether the acetal or aldehyde substrate is used.

    29. Niobium Complexes

      An Organotransition-Metal Complex with Pentagonal-Pyramidal Structure (pages 8046–8049)

      Dr. M. Angeles García-Monforte, Dr. Miguel Baya, Prof. Dr. Larry R. Falvello, Dr. Antonio Martín and Dr. Babil Menjón

      Article first published online: 29 JUN 2012 | DOI: 10.1002/anie.201202819

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      Star gazing: The six-coordinate organoniobium(V) compound [NBu4]2[NbO(C6F5)5] has been found to exhibit a pentagonal-pyramidal (PPY-6) structure, which is unprecedented in organotransition-metal chemistry (see picture: complex as viewed down the O–Nb axis; C in gray, O in red, F in yellow, and Nb in blue).

    30. Redox Chemistry

      Visible-Light-Promoted C[BOND]C Bond Cleavage: Photocatalytic Generation of Iminium Ions and Amino Radicals (pages 8050–8053)

      Shunyou Cai, Xinyang Zhao, Xinbo Wang, Qisong Liu, Prof. Dr. Zigang Li and Prof. Dr. David Zhigang Wang

      Article first published online: 3 JUL 2012 | DOI: 10.1002/anie.201202880

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      Photoscissors: Structurally variable and synthetically robust iminium ions and amino radicals species could be simultaneously generated by visible-light-promoted photoredox cleavage of the C[BOND]C bonds in simple vicinal diamine precursors under very mild reaction conditions.

    31. Microfluidic Reactor Imaging

      Characterization of Microfluidic Gas Reactors Using Remote-Detection MRI and Parahydrogen-Induced Polarization (pages 8054–8058)

      Dr. Vladimir V. Zhivonitko, Dr. Ville-Veikko Telkki and Prof. Igor V. Koptyug

      Article first published online: 2 JUL 2012 | DOI: 10.1002/anie.201202967

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      A substantial boost in sensitivity (almost 105-fold) achieved by combining remote-detection MRI and parahydrogen-induced polarization enabled microfluidic reactor imaging. Quantitative estimates of nuclear spin hyperpolarization, reaction product distribution, mass transport, and adsorption in the microfluidic reactors could thus be determined in situ. The reactors also serve as microfluidic nuclear spin polarizers.

    32. Aziridination

      Hypoiodite-Mediated Metal-Free Catalytic Aziridination of Alkenes (pages 8059–8062)

      Dr. Akira Yoshimura, Kyle R. Middleton, Chenjie Zhu, Prof. Dr. Victor N. Nemykin and Prof. Dr. Viktor V. Zhdankin

      Article first published online: 2 JUL 2012 | DOI: 10.1002/anie.201203925

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      Look, no metal: A metal-free catalytic procedure for aziridination of alkenes using tetrabutylammonium iodide as the catalyst, m-chloroperoxybenzoic acid (mCPBA) as the terminal oxidant, and N-aminophthalimide as the nitrenium precursor has been developed (see scheme; right: X-ray structure of one of the products). Control experiments suggests that the active oxidant is in situ generated hypoiodous acid (HIO).

    33. Zinc Catalysis

      Catalytic Generation of Zinc Carbenes from Alkynes: Zinc-Catalyzed Cyclopropanation and Si[BOND]H Bond Insertion Reactions (pages 8063–8067)

      Dr. Rubén Vicente, Jesús González, Dr. Lorena Riesgo, Dr. Javier González and Dr. Luis A. López

      Article first published online: 29 JUN 2012 | DOI: 10.1002/anie.201203914

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      Think zinc: Synthetically relevant zinc(II) carbenes are catalytically generated from alkynes (see scheme). This new approach allows zinc-catalyzed cyclopropanation and Si[BOND]H bond insertion reactions to generate the corresponding cyclopropylfurans or silane derivatives. The structure of the key carbene intermediate was studied using theoretical methods.

    34. Electrochemiluminescence Imaging

      Imaging Latent Fingerprints by Electrochemiluminescence (pages 8068–8072)

      Linru Xu, Yan Li, Suozhu Wu, Xianghong Liu and Dr. Bin Su

      Article first published online: 2 JUL 2012 | DOI: 10.1002/anie.201203815

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      By exposing an electrode surface with a latent fingerprint to electrochemiluminescence (ECL)-generating luminophore, ECL is produced from the surface not covered by the fingerprint, generating a negative image (see picture, left). The fingerprint can also be pre-stained by luminophores, which generates ECL and yields a positive image (right). ITO=indium tin oxide.

    35. Synthetic Methods

      Gallium Tribromide Catalyzed Coupling Reaction of Alkenyl Ethers with Ketene Silyl Acetals (pages 8073–8076)

      Dr. Yoshihiro Nishimoto, Hiroki Ueda, Dr. Makoto Yasuda and Prof. Dr. Akio Baba

      Article first published online: 2 JUL 2012 | DOI: 10.1002/anie.201203778

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      A ‘Ga'llant couple: The α-alkenylation of esters was accomplished by GaBr3-catalyzed coupling between alkenyl ethers and ketene silyl acetals. In this reaction system, various alkenyl ethers, including those with vinyl and substituted alkenyl groups, were applicable, and the scope of applicable ketene silyl acetals was sufficiently broad. The mechanism is also discussed.

    36. C[BOND]H Amination

      Selective Iodine-Catalyzed Intermolecular Oxidative Amination of C(sp3)[BOND]H Bonds with ortho-Carbonyl-Substituted Anilines to Give Quinazolines (pages 8077–8081)

      Dr. Yizhe Yan, Yonghui Zhang, Dr. Chengtao Feng, Prof. Zhenggen Zha and Prof. Dr. Zhiyong Wang

      Article first published online: 2 JUL 2012 | DOI: 10.1002/anie.201203880

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      Access to quinazolines: The selective amination of C(sp3)[BOND]H bonds adjacent to nitrogen or oxygen atoms of N-alkylamides, ethers, or alcohols with ortho-carbonyl-substituted anilines constitutes the first step in a tandem annulation that leads to quinazolines in good to excellent yields (see scheme; NIS=N-Iodosuccinimide, TBHP=tert-butyl hydroperoxide). The selectivity of the amination of primary and secondary C[BOND]H bonds is also noteworthy (left: >3:1, right: >99:1).

    37. Biomass Conversion

      Deoxygenation of Biomass-Derived Feedstocks: Oxorhenium-Catalyzed Deoxydehydration of Sugars and Sugar Alcohols (pages 8082–8086)

      Mika Shiramizu and Prof. F. Dean Toste

      Article first published online: 4 JUL 2012 | DOI: 10.1002/anie.201203877

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      Turn sugar into oil: The deoxygenation reaction of sugar moieties is important for the conversion of biomass into chemicals and fuels. The methyltrioxorhenium-catalyzed deoxydehydration reaction was successfully applied to this purpose using another alcohol as solvent/reductant. The reaction was highly stereospecific, affording linear polyene products from C4–C6 sugar alcohols and aromatic compounds from C4–C6 sugars.

    38. Main-Group Chemistry

      Cyclic Distiba- and Dibismadiazenium Cations (pages 8087–8091)

      Mathias Lehmann, Prof. Dr. Axel Schulz and Dr. Alexander Villinger

      Article first published online: 5 JUL 2012 | DOI: 10.1002/anie.201203267

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      Think positive, keep the anions away: Hitherto unknown mono- and dications of the type [XE(μ-NTerE)]+ and [E2(μ-NTer)2]2+ (E=Sb, Bi; X=Cl, I) were studied and fully characterized for the first time. Salts bearing these highly reactive cations can be obtained from terphenyl-substituted cyclo-dipnictadiazanes [XE(μ-NR)]2 by halide abstraction or triflate substitution.

    39. C[BOND]H Functionalization

      Rhodium(III)-Catalyzed Dehydrogenative Heck Reaction of Salicylaldehydes (pages 8092–8096)

      Dr. Zhuangzhi Shi, Nils Schröder and Prof. Dr. Frank Glorius

      Article first published online: 28 JUN 2012 | DOI: 10.1002/anie.201203224

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      Your CHOice! An efficient RhIII-catalyzed dehydrogenative Heck reaction (DHR) of salicylaldehydes with different classes of olefins extends the oxidative Heck reaction to aldehyde C[BOND]H bonds. Several structural motifs similar to natural products and bioactive molecules such as aurones, flavones, 2′-hydroxychalcones, and flavanones could be efficiently produced. Initial mechanistic studies give insight into the reaction mechanism.

    40. C[BOND]H Activation

      Intramolecular C[BOND]H Bond Activation through a Flexible Ester Linkage (pages 8097–8100)

      Dr. Christopher J. Shaffer, Dr. Detlef Schröder, Christoph Gütz and Prof. Dr. Arne Lützen

      Article first published online: 2 JUL 2012 | DOI: 10.1002/anie.201203163

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      Replacing the director: A bipyridinyl ligand with an aliphatic side chain determines the regioselectivity of copper-catalyzed C[BOND]H oxidation by intramolecular effects. Because the aliphatic chain is attached through an ester linkage, the catalytic cycle can in principle be closed by transesterification. Ion-mobility mass spectrometry and isotopic labeling provide mechanistic insight not available from direct mass spectrometry experiments.

    41. Allylzinc Monocation

      Dimerization of the Allylzinc Cation: Selective Coupling of Allyl Anions in a Metallo-Ene Reaction (pages 8101–8105)

      Dipl.-Chem. Crispin Lichtenberg, Dr. Thomas P. Spaniol and Prof. Dr. Jun Okuda

      Article first published online: 3 JUL 2012 | DOI: 10.1002/anie.201203698

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      Metal assistance: Dimerization of the allylzinc monocation gives the dimetalated coupling product in quantitative yield (see scheme). Kinetic and thermodynamic parameters of this reversible metallo-ene reaction have been determined. This reaction serves as a model system for the alkali-metal catalyzed production of 4-methylpentene.

    42. Low-Dimensional Conductors

      A Semiconductor or A One-Dimensional Metal and Superconductor through Tellurium π Stacking (pages 8106–8109)

      Dr. Ejaz Ahmed, Prof. Dr. Johannes Beck, Dr. Jörg Daniels, Prof. Dr. Thomas Doert, Dr. Steffen Jan Eck, Dr. Andreas Heerwig, Dr. Anna Isaeva, Prof. Dr. Sven Lidin, Prof. Dr. Michael Ruck, Dr. Walter Schnelle and Dr. Alexander Stankowski

      Article first published online: 4 JUL 2012 | DOI: 10.1002/anie.201200895

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      One-dimensional conductor: Strong π interactions between ecliptically stacked tellurium squares in Te4[Bi0.74Cl4] trigger excellent one-dimensional metallic conductivity as well as superconductivity below 7.15 K under ambient pressure. The electron-precise counterpart, Te4[Bi0.67Cl4], is a semiconductor. The bismuth content and temperature- dependent competition of intra- and inter-ring bonding account for the electronic conduction.

    43. CXCR4 Ligands

      A Conformationally Frozen Peptoid Boosts CXCR4 Affinity and Anti-HIV Activity (pages 8110–8113)

      Dr. Oliver Demmer, Dr. Andreas O. Frank, Dr. Franz Hagn, Dr. Margret Schottelius, Prof. Dr. Luciana Marinelli, Dr. Sandro Cosconati, Prof. Dr. Ruth Brack-Werner, Dr. Stephan Kremb, Prof. Dr. Hans-Jürgen Wester and Prof. Dr. Horst Kessler

      Article first published online: 3 JUL 2012 | DOI: 10.1002/anie.201202090

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      There can be only one: Using a peptoid motif obtained by shifting the arginine side chain of a pentapeptide previously developed by Fujii et al. to the neighboring nitrogen atom restricts the conformational freedom and yields a conformationally homogeneous peptide (see picture) with a 100-fold higher binding affinity to the chemokine receptor CXCR4 in the picomolar range. Its efficiency to inhibit HIV-1 infections is also demonstrated.

    44. Spectroelectrochemistry

      Combined Electrochemistry and Surface-Enhanced Infrared Absorption Spectroscopy of Gramicidin A Incorporated into Tethered Bilayer Lipid Membranes (pages 8114–8117)

      Jacek Kozuch, Prof. Dr. Claudia Steinem, Prof. Dr. Peter Hildebrandt and Dr. Diego Millo

      Article first published online: 2 JUL 2012 | DOI: 10.1002/anie.201203214

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      Support from the support: Tethered bilayer lipid membranes containing the cation-channel-forming peptide gramicidin A were assembled on nanostructured Au films. The combination of surface-enhanced infrared absorption (SEIRA) and electrochemical impedance spectroscopy (EIS) was used for the in situ structural and functional characterization of gramicidin A in the same device.

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