Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 19

May 5, 2014

Volume 53, Issue 19

Pages 4727–4975

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Flashback
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. You have free access to this content
      Cover Picture: A New Pathway of DNA G-Quadruplex Formation (Angew. Chem. Int. Ed. 19/2014) (page 4727)

      Dr. Slavko Čeru, Dr. Primož Šket, Dr. Iztok Prislan, Prof. Dr. Jurij Lah and Prof. Dr. Janez Plavec

      Version of Record online: 3 APR 2014 | DOI: 10.1002/anie.201401133

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      Guanine-rich DNA sequences can self-assemble into specific pre-organized DNA structures, where two-by-two guanine residues shown as “duets” are involved in GG N1-carbonyl symmetric base pairs. In their Communication on page 4881 ff., J. Lah, J. Plavec, and co-workers demonstrate the transition of these “duets” into guanine-quartets, presented as a “string quartet” when interacting with cations, such as potassium ions. This rearrangement consequently leads to formation of G-quadruplex structures.

    2. You have free access to this content
      Inside Cover: Room-Temperature Carbide-Derived Carbon Synthesis by Electrochemical Etching of MAX Phases (Angew. Chem. Int. Ed. 19/2014) (page 4728)

      Maria R. Lukatskaya, Joseph Halim, Boris Dyatkin, Michael Naguib, Yulia S. Buranova, Prof. Michel W. Barsoum and Prof. Yury Gogotsi

      Version of Record online: 9 APR 2014 | DOI: 10.1002/anie.201403559

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      The electrochemically induced extraction of metal atoms from the ternary layered carbides Ti3AlC2, Ti2AlC, and Ti3SiC2 (MAX phases) at room temperature results in predominantly amorphous carbon with a narrow distribution of micropores, as described by Y. Gogotsi et al. in their Communication on page 4877 ff. This approach forgoes energy-intensive thermal processing and presents a novel method for the synthesis of carbon materials that may be used as supercapacitors, battery electrodes, or for CO2 capture.

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      Inside Back Cover: Controlled Electropolymerization of Ruthenium(II) Vinylbipyridyl Complexes in Mesoporous Nanoparticle Films of TiO (Angew. Chem. Int. Ed. 19/2014) (page 4977)

      Dr. Zhen Fang, Dr. Shahar Keinan, Dr. Leila Alibabaei, Hanlin Luo, Dr. Akitaka Ito and Prof. Dr. Thomas J. Meyer

      Version of Record online: 2 APR 2014 | DOI: 10.1002/anie.201403679

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      Electrochemically controlled radical polymerization enabled the growth of ruthenium(II) vinylpolypyridyl complexes within the cavities of TiO2 films, as described by T. J. Meyer et al. in their Communication on page 4872 ff. The in situ prepared film is of potential for harvesting light in dye-sensitized solar cells and in dye-sensitized photoelectrosynthesis cells that operate in an aqueous environment.

    4. You have free access to this content
      Back Cover: Towards True Carbaporphyrinoids: Synthesis of 21-Carba-23-thiaporphyrin (Angew. Chem. Int. Ed. 19/2014) (page 4978)

      Dr. Anna Berlicka, Paweł Dutka, Dr. Ludmiła Szterenberg and Prof. Lechosław Latos-Grażyński

      Version of Record online: 15 APR 2014 | DOI: 10.1002/anie.201401138

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      Replacement of a single pyrrole ring by a cyclopentadiene fragment appears to be a compelling strategy for the creation of true carbaporphyrins, which can be regarded as fundamental extensions of the classical porphyrinic motif. In their Communication on page 4885 ff., L. Latos-Grażyński and co-workers describe the rational approach that allowed incorporation of an unsubstituted cyclopentadiene instead of a pyrrole ring in a heteroporphyrin framework to form 21-carbathiaporphyrin, the first meso-substituted true carbaporphyrinoid.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Flashback
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. You have free access to this content
      Frontispiece: Particle Display: A Quantitative Screening Method for Generating High-Affinity Aptamers

      Jinpeng Wang, Qiang Gong, Nupur Maheshwari, Michael Eisenstein, Mary Luz Arcila, Kenneth S. Kosik and Prof. H. Tom Soh

      Version of Record online: 2 MAY 2014 | DOI: 10.1002/anie.201481971

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      A new particle display method for aptamer screening is described by H. T. Soh and co-workers in their Communication on page 4796 ff. High-quality aptamers can be generated rapidly and economically by this approach.

  3. Editorial

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Flashback
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. You have free access to this content
  4. Graphical Abstract

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Flashback
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. 50 Years Ago ... (page 4740)

      Version of Record online: 2 MAY 2014 | DOI: 10.1002/anie.201401127

  6. Author Profile

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Flashback
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Akira Sekiguchi (page 4746)

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/anie.201310966

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      “My favorite food is shellfish such as lobster and crab. If I won the lottery, I would take a luxury cruise and travel around the world …” This and more about Akira Sekiguchi can be found on page 4746.

  7. Book Review

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Flashback
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Transition-Metal-Mediated Aromatic Ring Construction. Edited by Ken Tanaka. (page 4747)

      Hervé Clavier

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201400611

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      John Wiley & Sons, Hoboken, 2013. 830 pp., hardcover, € 152.00.—ISBN 978-1118148921

  8. Highlights

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Flashback
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Cytochrome P450

      19582014: After 56 Years of Research, Cytochrome P450 Reactivity Is Finally Explained (pages 4750–4752)

      Ashley B. McQuarters, Matthew W. Wolf, Andrew P. Hunt and Dr. Nicolai Lehnert

      Version of Record online: 7 APR 2014 | DOI: 10.1002/anie.201402404

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      Nature's wisdom in enzyme design: Compounds I and II in the catalytic cycle of the Cytochrome P450 enzymes have been trapped and characterized recently. This work has provided further insight into the electronic structure and reactivity of these crucial intermediates, and key questions regarding the mechanism of these enzymes have finally been answered.

    2. Phosphorus Compounds

      New Phosphorus Analogues of Nitrogen Classics—No Carbon Copies (pages 4753–4754)

      Prof. Dr. Dietrich Gudat

      Version of Record online: 9 APR 2014 | DOI: 10.1002/anie.201400762

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      Getting heavy: The recently prepared phosphorus analogues of two old acquaintances, urea and dinitrogen tetroxide, bear some structural resemblance to their archetypes but are no carbon copies. Their syntheses and chemical properties reveal rather certain peculiarities, which back the doctrine that the electronic properties of the heavier elements in a group differ from those of the lightest congener.

  9. Review

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Flashback
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Spectroscopic Methods

      Surface-Enhanced Raman Spectroscopy: Concepts and Chemical Applications (pages 4756–4795)

      Prof. Dr. Sebastian Schlücker

      Version of Record online: 7 APR 2014 | DOI: 10.1002/anie.201205748

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      Expanding vibrational spectroscopy: Since its first observation in 1973, surface-enhanced Raman scattering (SERS) has developed into a mature vibrational spectroscopic technique. The number of applications in chemistry as well as the material and life sciences is increasing rapidly. This Review summarizes the key concepts behind SERS and provides an overview of current applications in chemistry.

  10. Communications

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Editorial
    5. Graphical Abstract
    6. Flashback
    7. Author Profile
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. High-Throughput Aptamer Screening

      Particle Display: A Quantitative Screening Method for Generating High-Affinity Aptamers (pages 4796–4801)

      Jinpeng Wang, Qiang Gong, Nupur Maheshwari, Michael Eisenstein, Mary Luz Arcila, Kenneth S. Kosik and Prof. H. Tom Soh

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201309334

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      Superior aptamers can be obtained in fewer selection rounds with the particle display method than with the conventional approach. In this new method libraries of solution-phase aptamers are transformed into “aptamer particles”, each displaying many copies of a single sequence on its surface. Fluorescence-activated cell sorting is then used to individually measure the relative affinities of >108 aptamer particles and sort them in a high-throughput manner.

    2. C[BOND]H Functionalization

      Late-Stage Functionalization of Biologically Active Heterocycles Through Photoredox Catalysis (pages 4802–4806)

      Dr. Daniel A. DiRocco, Kevin Dykstra, Dr. Shane Krska, Dr. Petr Vachal, Donald V. Conway and Dr. Matthew Tudge

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/anie.201402023

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      Search and find: A method has been developed for the direct methyl-, ethyl-, and cyclopropylation of biologically active heterocycles using visible-light photoredox catalysis. High-throughput experimentation was used to discover the best catalyst. The simple protocol, mild reaction conditions, and unique tolerability make this method a valuable tool for drug discovery.

    3. Gold Carbenoids

      Structure of a Reactive Gold Carbenoid (pages 4807–4811)

      Ing. Günter Seidel and Prof. Alois Fürstner

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201402080

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      Call me “carbenoid”: No signs of significant Au[BOND]C double-bond character, but many indications for charge density at carbon distinguish the structure of an only modestly “stabilized” gold carbenoid in the solid state. Because this species is capable of cyclopropanating a styrene derivative under mild conditions, its structural features are relevant for mechanistic discussions of π-acid catalysis in general.

    4. Drug Delivery

      In Vivo Chemoembolization and Magnetic Resonance Imaging of Liver Tumors by Using Iron Oxide Nanoshell/Doxorubicin/Poly(vinyl alcohol) Hybrid Composites (pages 4812–4815)

      Prof. Dr. Yi-Xiang J. Wang, Dr. Xiao-Ming Zhu, Qi Liang, Prof. Dr. Christopher H. K. Cheng, Prof. Dr. Wei Wang and Prof. Dr. Ken Cham-Fai Leung

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201402144

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      Therapeutic cut off: A hybrid composite based on superparamagnetic iron oxide nanoshells/doxorubicin/poly(vinyl alcohol) (shown in black/blue/red) was used for the in vivo embolization of liver tumor blood vessels. Disassembly of the composite followed, thereby leading to slow and sustained release of the anticancer drug. The composite was relatively noncytotoxic and was responsive to magnetic resonance imaging, thus making it a potential theranostic agent.

    5. Solar Cells

      Constructing 3D Branched Nanowire Coated Macroporous Metal Oxide Electrodes with Homogeneous or Heterogeneous Compositions for Efficient Solar Cells (pages 4816–4821)

      Wu-Qiang Wu, Yang-Fan Xu, Hua-Shang Rao, Hao-Lin Feng, Prof. Dr. Cheng-Yong Su and Prof. Dr. Dai-Bin Kuang

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/anie.201402371

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      Wired for light: A versatile method allows the preparation of nanowire-coated macroporous material based homo- or heterogeneous metal oxide composite electrodes (TiO2–TiO2, SnO2–TiO2, and Zn2SnO4–TiO2). Dye-sensitized solar cells based on macroporous TiO2/TiO2 nanowire homogeneous electrode show an impressive conversion efficiency as high as 9.51 %, which is much higher than those of pure macroporous material based photoelectrodes used up to date.

    6. Nanoporous Graphene

      High-Quality Three-Dimensional Nanoporous Graphene (pages 4822–4826)

      Dr. Yoshikazu Ito, Dr. Yoichi Tanabe, Dr. H.-J. Qiu, Dr. Katsuaki Sugawara, Dr. Satoshi Heguri, Dr. Ngoc Han Tu, Dr. Khuong Kim Huynh, Dr. Takeshi Fujita, Prof. Takashi Takahashi, Prof. Katsumi Tanigaki and Prof. Mingwei Chen

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/anie.201402662

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      A nickel for your graphene: The title material was synthesized by chemical vapor deposition using nanoporous nickel. The 3D nanoporous graphene preserves 2D electronic properties, such as high electron mobility and massless Dirac fermions.

    7. Smart Materials

      Optical Devices Constructed from Multiresponsive Microgels (pages 4827–4831)

      Dr. Qiang Matthew Zhang, Wenwen Xu and Prof. Michael J. Serpe

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/anie.201402641

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      A microgel-based etalon that is capable of changing its optical properties in response to light, solutions of various pHs, and exposure to nerve agents is reported. This investigation showcases the versatility of the etalon construct, which can be made multiresponsive simply by changing the chemistry of its polymer makeup.

    8. Bonding

      Confirmed by X-ray Crystallography: The B⋅B One-Electron σ Bond (pages 4832–4835)

      M. Sc. Alexander Hübner, B. Sc. Andreas M. Diehl, Dr. Martin Diefenbach, Dr. Burkhard Endeward, Dr. Michael Bolte, Dr. Hans-Wolfram Lerner, Prof. Dr. Max C. Holthausen and Prof. Dr. Matthias Wagner

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201402158

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      One is enough: The first structurally characterized radical anion containing a B⋅B one-electron σ bond shows a significantly shorter B⋅⋅⋅B distance than the uncharged starting material, while the boron centers largely maintain their local planarity.

    9. Drug Discovery

      Total Synthesis of Syringolin A and Improvement of Its Biological Activity (pages 4836–4839)

      Takuya Chiba, Hidetaka Hosono, Koji Nakagawa, Masahiro Asaka, Hiroshi Takeda, Akira Matsuda and Satoshi Ichikawa

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201402428

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      Fine-tuned activity: The total synthesis of syringolin A (1) was established by an intramolecular Ugi three-component reaction. To improve the moderate biological activities of 1, analogues having strong proteasome inhibitory and cytotoxic activities comparable to clinically used bortezomib, were prepared.

    10. Biosynthesis

      Mechanistic Insights into Polycycle Formation by Reductive Cyclization in Ikarugamycin Biosynthesis (pages 4840–4844)

      Dr. Guangtao Zhang, Dr. Wenjun Zhang, Dr. Qingbo Zhang, Ting Shi, Liang Ma, Dr. Yiguang Zhu, Dr. Sumei Li, Dr. Haibo Zhang, Prof. Dr. Yi-Lei Zhao, Prof. Dr. Rong Shi and Prof. Dr. Changsheng Zhang

      Version of Record online: 6 APR 2014 | DOI: 10.1002/anie.201402078

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      Polycycle formation: The mechanism of a five-membered-ring formation in polycyclic tetramate macrolactams (PTMs; see picture) was demonstrated by exploring the IkaC-catalyzed reductive cyclization in ikarugamycin biosynthesis, using a Michael addition-like reaction. This study suggested a general strategy for polycycle formation in PTMs.

    11. Enzyme Catalysis

      Entropy is Key to the Formation of Pentacyclic Terpenoids by Enzyme-Catalyzed Polycyclization (pages 4845–4849)

      Dr. Per-Olof Syrén, Stephan C. Hammer, Dr. Birgit Claasen and Prof. Dr. Bernhard Hauer

      Version of Record online: 7 APR 2014 | DOI: 10.1002/anie.201402087

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      Disorderly conduct: Through theoretical and experimental work with a thermophilic triterpene cyclase, it was demonstrated that entropy is key to the polycyclizations that it catalyzes. The release of water molecules (red) through specific channels allows for the prefolding of the polyisoprene substrate (purple) and thus the generation of multicyclic scaffolds by terpene cyclase enzymes.

    12. Polymer Films

      Controlled Synthesis of Conjugated Microporous Polymer Films: Versatile Platforms for Highly Sensitive and Label-Free Chemo- and Biosensing (pages 4850–4855)

      Dr. Cheng Gu, Ning Huang, Jia Gao, Fei Xu, Dr. Yanhong Xu and Prof. Dr. Donglin Jiang

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201402141

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      Exceptionally thin: Electropolymerization was employed for the synthesis of conjugated microporous polymer (CMP) films on substrates or as freestanding thin films. The method enables the control of the thickness, size, and shape of the CMP films, which can function as versatile platforms for highly sensitive and label-free chemo- and biosensing, featuring rapid response, excellent selectivity, and reusability.

    13. Surface Chemistry

      Crystal-Plane-Controlled Selectivity of Cu2O Catalysts in Propylene Oxidation with Molecular Oxygen (pages 4856–4861)

      Qing Hua, Tian Cao, Dr. Xiang-Kui Gu, Prof. Dr. Jiqing Lu, Dr. Zhiquan Jiang, Xiaorong Pan, Liangfeng Luo, Prof. Dr. Wei-Xue Li and Prof. Dr. Weixin Huang

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201402374

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      Just plane favoritism: In the catalysis of propylene oxidation with O2 to acrolein, propylene oxide, and CO2, Cu2O octahedra with exposed {111} crystal planes favored the formation of acrolein, Cu2O cubes with exposed {100} crystal planes gave CO2 preferentially, and Cu2O rhombic dodecahedra with exposed {110} crystal planes gave a higher proportion of propylene oxide. The active sites for these reactions were identified as indicated in the scheme.

    14. Supramolecular Chemistry

      Modular Construction of Dynamic Nucleodendrimers (pages 4862–4866)

      Dr. Valentina Abet, Dr. Robert Evans, Florian Guibbal, Dr. Stefano Caldarelli and Dr. Raphaël Rodriguez

      Version of Record online: 2 APR 2014 | DOI: 10.1002/anie.201402400

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      Dendritic macromolecules: Isoguanosine-containing dendritic small molecules self-assemble into isoguanosine-containing dendrimers named nucleodendrimers (see picture). The building blocks alone form pentameric structures while the presence of alkali metals promotes the formation of stable decamers. This system provides a powerful canvas for the rapid and modular assembly of polyfunctional dendritic macromolecules.

    15. Vaccine Engineering

      Construction of a Live-Attenuated HIV-1 Vaccine through Genetic Code Expansion (pages 4867–4871)

      Nanxi Wang, Dr. Yue Li, Dr. Wei Niu, Dr. Ming Sun, Dr. Ronald Cerny, Prof. Qingsheng Li and Prof. Jiantao Guo

      Version of Record online: 8 APR 2014 | DOI: 10.1002/anie.201402092

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      Combat against AIDS: A novel unnatural amino acid (UAA*)-mediated amber codon (UAG) suppression strategy was used to precisely control HIV-1 viability in vitro (see picture). The resulting live-attenuated virus can be potentially used as HIV-1 vaccine.

    16. Oligomer Growth

      Controlled Electropolymerization of Ruthenium(II) Vinylbipyridyl Complexes in Mesoporous Nanoparticle Films of TiO2 (pages 4872–4876)

      Dr. Zhen Fang, Dr. Shahar Keinan, Dr. Leila Alibabaei, Hanlin Luo, Dr. Akitaka Ito and Prof. Dr. Thomas J. Meyer

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/anie.201402309

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      Growth on the surface: Ruthenium(II) vinylpolypyridyl assemblies within the cavities of mesoporous nanoparticle TiO2 films have been grown from the surface by stepwise, electrochemically controlled radical polymerization. This polymerization was monitored by cyclic voltammetry as well as UV/Vis and X-ray photoelectron spectroscopy.

    17. Carbon

      Room-Temperature Carbide-Derived Carbon Synthesis by Electrochemical Etching of MAX Phases (pages 4877–4880)

      Maria R. Lukatskaya, Joseph Halim, Boris Dyatkin, Michael Naguib, Yulia S. Buranova, Prof. Michel W. Barsoum and Prof. Yury Gogotsi

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201402513

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      A mild route to carbon: The formation of carbide-derived carbons (CDCs) by electrochemically induced extraction of metal atoms from ternary carbides at room temperature is demonstrated. This approach eschews high temperatures or the use of chlorine gas and allows for the formation of carbon films with quite narrow pore size distributions.

    18. Oligonucleotides

      A New Pathway of DNA G-Quadruplex Formation (pages 4881–4884)

      Dr. Slavko Čeru, Dr. Primož Šket, Dr. Iztok Prislan, Prof. Dr. Jurij Lah and Prof. Dr. Janez Plavec

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201400531

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      A new folding intermediate of Oxytricha nova telomeric Oxy-1.5 G-quadruplex was characterized in aqueous solution, where all guanine bases are involved in GG N1-carbonyl symmetric base pairs. G-rich DNA sequences can self-assemble into specific pre-organized DNA structures that are predisposed to fold into G-quadruplexes in the presence of cations such as potassium ions (see picture).

    19. Carbaporphyrinoids

      Towards True Carbaporphyrinoids: Synthesis of 21-Carba-23-thiaporphyrin (pages 4885–4889)

      Dr. Anna Berlicka, Paweł Dutka, Dr. Ludmiła Szterenberg and Prof. Lechosław Latos-Grażyński

      Version of Record online: 3 MAR 2014 | DOI: 10.1002/anie.201310999

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      A carbon pentagon in heteroporphyrin: The synthesis of a 21-carbathiachlorin followed by oxidation allowed construction of a 21-carbathiaporphyrin, a meso-substituted true carbaporphyrin with an unsubstituted cyclopentadienyl moiety (Mes=mesityl). Both carbathiaporphyrinoids act as aromatic cyclic ligands, as shown by their coordination to Pd2+ ions through their C, N, S donor atoms in the porphyrinic core.

    20. Supramolecular Chemistry

      A Collection of Fullerenes for Synthetic Access Toward Oriented Charge-Transfer Cascades in Triple-Channel Photosystems (pages 4890–4895)

      Dr. Altan Bolag, Javier López-Andarias, Santiago Lascano, Saeideh Soleimanpour, Dr. Carmen Atienza, Dr. Naomi Sakai, Prof. Nazario Martín and Prof. Stefan Matile

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201402042

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      Stacked up: With molecular-level precision, 1,4-diaryl-, methano-, and Bingel fullerenes are engineered into multicomponent architectures by surface-initiated ring-opening disulfide exchange polymerization and templated stack exchange with orthogonal dynamic covalent hydrazone chemistry (see scheme). The results validate the concept of building triple-channel photosystems with oriented strings of fullerenes for directional electron transport.

    21. Natural Product Synthesis

      You have full text access to this OnlineOpen article
      Gold(I) as an Artificial Cyclase: Short Stereodivergent Syntheses of (−)-Epiglobulol and (−)-4β,7α- and (−)-4α,7α-Aromadendranediols (pages 4896–4899)

      Dr. Javier Carreras, Madeleine Livendahl, Dr. Paul R. McGonigal and Prof. Antonio M. Echavarren

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201402044

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      Aromasynthesis: Aromadendrane sesquiterpenes (−)-epiglobulol, (−)-4α,7α-aromadendranediol, and (−)-4β,7α-aromadendranediol are synthesized in only seven steps from (E,E)-farnesol by a stereodivergent gold(I)-catalyzed cascade reaction.

    22. Gene Expression

      Bidirectional Regulation of mRNA Translation in Mammalian Cells by Using PUF Domains (pages 4900–4904)

      Jicong Cao, Dr. Manish Arha, Chaitanya Sudrik, Prof. David V. Schaffer and Prof. Ravi S. Kane

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/anie.201402095

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      One way or another: A genetically encoded system based on the RNA binding domain of PUF proteins was developed for the posttranscriptional regulation of gene expression. The PUF domain was used to tether a translational activation domain (eIF4E) to enhance translation. Alternatively, the PUF domain alone could be used to repress translation. The expression of a reporter could be varied by over 17-fold by using PUF-based activators and repressors.

    23. pH-Sensitive Microgels

      The Compressibility of pH-Sensitive Microgels at the Oil–Water Interface: Higher Charge Leads to Less Repulsion (pages 4905–4909)

      Dipl.-Chem. Karen Geisel, Prof. Dr. Lucio Isa and Prof. Dr. Walter Richtering

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/anie.201402254

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      More charge—less repulsion: The influence of electrostatic interactions on microgel-stabilized emulsions has been investigated on flat interfaces. The compressibility of charged microgels was found to be greater than for uncharged microgels, as the former start interacting effectively at a higher microgel density at the interface.

    24. Synthetic Methods

      Iron-Catalyzed 1,2-Addition of Perfluoroalkyl Iodides to Alkynes and Alkenes (pages 4910–4914)

      Dr. Tao Xu, Dr. Chi Wai Cheung and Prof. Dr. Xile Hu

      Version of Record online: 28 MAR 2014 | DOI: 10.1002/anie.201402511

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      An iron protocol: General and tolerant iron catalysis has been developed for the intermolecular 1,2-addition of perfluoroalkyl iodides to alkynes and alkenes. The resulting perfluoroalkylated alkyl and alkenyl iodides can be further functionalized by cross-coupling reactions.

    25. Natural Product Synthesis

      Accelerating Spirocyclic Polyketide Synthesis using Flow Chemistry (pages 4915–4920)

      Dr. Sean Newton, Dr. Catherine F. Carter, Dr. Colin M. Pearson, Leandro de C. Alves, Dr. Heiko Lange, Dr. Praew Thansandote and Prof. Steven V. Ley

      Version of Record online: 11 APR 2014 | DOI: 10.1002/anie.201402056

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      Rise of the machines: The syntheses of two spirocyclic polyketides, spirangien A methyl ester and spirodienal A, are described. This machine-assisted approach extends the application of flow chemistry to complex natural product synthesis and includes several flow-through processes of transformations commonly encountered in total synthesis.

    26. Photochemical Perfluoroalkylation

      Metal-Free Photochemical Aromatic Perfluoroalkylation of α-Cyano Arylacetates (pages 4921–4925)

      Manuel Nappi, Dr. Giulia Bergonzini and Prof. Dr. Paolo Melchiorre

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201402008

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      Shining light: An operationally simple protocol for the direct aromatic perfluoroalkylation and trifluoromethylation of α-cyano arylacetates requires the irradiation by visible light at ambient temperature. This metal-free reaction is driven by the photochemical activity of electron donor–acceptor (EDA) complexes, formed in situ by the interaction of transiently generated enolates and perfluoroalkyl iodides.

    27. Synthetic Methods

      Heterocycle Synthesis Based on Allylic Alcohol Transposition Using Traceless Trapping Groups (pages 4926–4929)

      Youwei Xie and Prof. Paul E. Floreancig

      Version of Record online: 7 APR 2014 | DOI: 10.1002/anie.201402010

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      Without a trace: Allylic alcohols transpose in the presence of Re2O7 and are trapped by aldehydes or ketones to form hemiacetals. Additional ionization yields oxocarbenium ions, which can be quenched through bimolecular reactions with nucleophiles to provide heterocycles with no trace of the initial trapping group. This method allows stereocontrol in the absence of chiral reagents and without recourse to protecting or leaving groups.

    28. Iron Catalysis

      Well-Defined Four-Coordinate Iron(II) Complexes For Intramolecular Hydroamination of Primary Aliphatic Alkenylamines (pages 4930–4934)

      Dr. Elise Bernoud, Dr. Pascal Oulié, Dr. Régis Guillot, Dr. Mohamed Mellah and Dr. Jérôme Hannedouche

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201402089

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      Iron horseshoe: A well-defined four-coordinate β-diketiminatoiron(II) alkyl complex is a precatalyst for the highly selective cyclohydroamination of primary aliphatic alkenylamines at mild temperatures. Its mechanism is also elucidated.

    29. Cu2O2 Equilibrium

      Observation of a CuII2(μ-1,2-peroxo)/CuIII2(μ-oxo)2 Equilibrium and its Implications for Copper–Dioxygen Reactivity (pages 4935–4939)

      Dr. Matthew T. Kieber-Emmons, Jake W. Ginsbach, Dr. Patrick K. Wick, Dr. Heather R. Lucas, Dr. Matthew E. Helton, Dr. Baldo Lucchese, Prof. Masatatsu Suzuki, Prof. Andreas D. Zuberbühler, Prof. Kenneth D. Karlin and Prof. Edward I. Solomon

      Version of Record online: 2 APR 2014 | DOI: 10.1002/anie.201402166

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      A copper system has been uncovered in which an end-on peroxo [Cu2(O2)] core is in equilibrium with a bis-μ-oxo [Cu2(O)2] core. Calibration of computational methods to experimental thermodynamic results suggest that the electrophilic reactivity patterns recently attributed to an end-on-peroxo CuII2 species are, in fact, likely a result of an accessible bis-μ-oxo CuIII2 core, a structural type long associated with electrophilic reactivity.

    30. Synthetic Methods

      Construction of Chiral Bridged Tricyclic Benzopyrans: Enantioselective Catalytic Diels–Alder Reaction and a One-Pot Reduction/Acid-Catalyzed Stereoselective Cyclization (pages 4940–4944)

      Aiguo Song, Dr. Xishuai Zhang, Xixi Song, Xiaobei Chen, Chenguang Yu, He Huang, Prof. Dr. Hao Li and Prof. Dr. Wei Wang

      Version of Record online: 24 MAR 2014 | DOI: 10.1002/anie.201402170

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      The old one-two: A two-step synthetic strategy was developed for the construction of the bridged benzopyran core present in many natural products. It consisted of an efficient asymmetric catalytic decarboxylative Diels–Alder reaction between enals and coumarin-3-carboxylic acids, and a one-pot protocol for the reduction/acid-catalyzed stereoselective cyclization. TBS=tert-butyldimethylsilyl.

    31. C(sp3)[BOND]H Activation

      Palladium-Catalyzed C(sp3)[BOND]H Activation: A Facile Method for the Synthesis of 3,4-Dihydroquinolinone Derivatives (pages 4945–4949)

      Jia-Xuan Yan, Dr. Hu Li, Dr. Xiang-Wei Liu, Jiang-Ling Shi, Xin Wang and Prof. Dr. Zhang-Jie Shi

      Version of Record online: 6 APR 2014 | DOI: 10.1002/anie.201402562

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      3,4-Dihydroquinolinones were synthesized by the palladium-catalyzed, oxidative-addition-initiated activation and arylation of inert C(sp3)[BOND]H bonds. Pd(OAc)2 and P(o-tol)3 were used as the catalyst and ligand, respectively, to improve the efficiency of the reaction. A further advantage of this reaction is that it could be performed in air.

    32. Heterocycles

      Manganese-Catalyzed Dehydrogenative [4+2] Annulation of N[BOND]H Imines and Alkynes by C[BOND]H/N[BOND]H Activation (pages 4950–4953)

      Ruoyu He, Prof. Dr. Zhi-Tang Huang, Prof. Dr. Qi-Yu Zheng and Prof. Dr. Congyang Wang

      Version of Record online: 2 APR 2014 | DOI: 10.1002/anie.201402575

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      Hidden talents: The ability of manganese(I) to catalytically induce C[BOND]H and N[BOND]H bond cleavage, and C[BOND]C and C[BOND]N bond formation, has been recognized using the title reaction. The reaction produces H2 as the major by-product and eliminates the need for any oxidants, external ligands, or additives, and thus tolerating a wide range of functionalities.

    33. Asymmetric Catalysis

      Construction of Quaternary Stereogenic Carbon Centers through Copper-Catalyzed Enantioselective Allylic Cross-Coupling with Alkylboranes (pages 4954–4958)

      Kentaro Hojoh, Yoshinori Shido, Prof. Dr. Hirohisa Ohmiya and Prof. Dr. Masaya Sawamura

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201402386

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      The SN2′-type: A combination of a chiral CuI/L* catalyst system and EtOK enabled the enantioselective SN2′-type allylic cross-coupling between alkylboranes and γ,γ-disubstituted primary allyl chlorides. The reaction generates quaternary carbon stereogenic centers bearing three sp3-alkyl groups and a vinyl group. A reaction pathway involving addition/elimination of a neutral alkylcopper(I) species is proposed.

    34. Heterocycles

      Gold-Catalyzed Synthesis of Functionalized Pyridines by Using 2H-Azirines as Synthetic Equivalents of Alkenyl Nitrenes (pages 4959–4963)

      Dr. Agnes Prechter, Guilhem Henrion, Pierre Faudot dit Bel and Fabien Gagosz

      Version of Record online: 8 APR 2014 | DOI: 10.1002/anie.201402470

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      Ringing the changes: A series of easily accessible 2-propargyl 2H-azirine derivatives were efficiently converted into the corresponding functionalized pyridines in the presence of a gold catalyst. This transformation, which exhibits a high functional-group tolerance and a wide substrate scope, corresponds to the formal intramolecular transfer of an alkenyl nitrene to an alkyne.

    35. Asymmetric 1,2-Addition

      Enantioselective Addition of Silicon Nucleophiles to Aldimines Using a Preformed NHC–Copper(I) Complex as the Catalyst (pages 4964–4967)

      Alexander Hensel, Dr. Kazuhiko Nagura, Lukas B. Delvos and Prof. Dr. Martin Oestreich

      Version of Record online: 3 APR 2014 | DOI: 10.1002/anie.201402086

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      The final chapter: The enantioselective addition of silicon nucleophiles to typical prochiral acceptors is now well-established methodology, except for the 1,2-addition to imines. McQuade's chiral NHC–copper(I) complex catalyzes this elusive transformation with high asymmetric induction, finally allowing for the catalyst-controlled preparation of α-silylated amines from aldimines (see scheme).

    36. Synthetic Methods

      Hydrocarbation of C[TRIPLE BOND]C Bonds: Quantification of the Nucleophilic Reactivity of Ynamides (pages 4968–4971)

      M. Sc. Hans A. Laub, Prof. Dr. Gwilherm Evano and Prof. Dr. Herbert Mayr

      Version of Record online: 8 APR 2014 | DOI: 10.1002/anie.201402055

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      Carbenium ions are isoelectronic with boranes, but hydrocarbations analogous to hydroborations usually do not occur. The hydrocarbation of ynamides with benzhydrylium ions and the difference to hydroborations are discussed. Furthermore, kinetic studies allowed the inclusion of ynamides in the comprehensive benzhydrylium-based nucleophilicity scale.

    37. Nanoreactors

      Tea-Bag-Like Polymer Nanoreactors Filled with Gold Nanoparticles (pages 4972–4975)

      Fabian Mitschang, Dr. Holger Schmalz, Prof. Dr. Seema Agarwal and Prof. Dr. Andreas Greiner

      Version of Record online: 2 APR 2014 | DOI: 10.1002/anie.201402212

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      Gold-containing polymer nanotubes were prepared by the “tubes by fiber templates” (TUFT) process. For this purpose, electrospun polymer nanofibers with incorporated gold nanoparticles were coated with poly(p-xylylene) by chemical vapor deposition and then the inner fiber templates were removed. The resulting tubes, which were utilized as a reusable tea-bag-like catalyst, showed pronounced catalytic activity and resistance to leaching.

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