Angewandte Chemie International Edition

Cover image for Vol. 51 Issue 51

December 14, 2012

Volume 51, Issue 51

Pages 12629–12896

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. You have free access to this content
      Cover Picture: Directed Assembly of Inorganic Polyoxometalate-based Micrometer-Scale Tubular Architectures by Using Optical Control (Angew. Chem. Int. Ed. 51/2012) (page 12629)

      Dr. Geoffrey J. T. Cooper, Richard W. Bowman, E. Peter Magennis, Dr. Francisco Fernandez-Trillo, Prof. Cameron Alexander, Prof. Miles J. Padgett and Prof. Leroy Cronin

      Article first published online: 5 DEC 2012 | DOI: 10.1002/anie.201209131

      Thumbnail image of graphical abstract

      The directed assembly and growth of polyoxometalate-based inorganic tube architectures using a computer-controlled laser-based system is described by L. Cronin, M. J. Padgett, et al. in their Communication on page 12754 ff. The picture shows the directed fusion of two tubes, colored red and green, on a microscope slide with the focus of the laser shown in red; the resulting network is made of hollow tubes that can act as microscopic flow channels.

    2. You have free access to this content
      Inside Cover: Vanadium Distribution in Four-Component Mo-V-Te-Nb Mixed-Oxide Catalysts from First Principles: How to Explore the Numerous Configurations? (Angew. Chem. Int. Ed. 51/2012) (page 12630)

      Gang Fu, Xin Xu and Philippe Sautet

      Article first published online: 23 NOV 2012 | DOI: 10.1002/anie.201209050

      Thumbnail image of graphical abstract

      Playing dice with Mo-V-Te-Nb oxide a promising catalyst for alkane oxidation with a structure obscured by the fractional distribution of V or Mo atoms on many sites. In their Communication on page 12854 ff., P. Sautet et al. present an efficient DFT approach that allows fast comparison of the energies of up to 8008 configurations of this complex oxide. The calculations predict the statistical V atom distribution found experimentally, when the dice are loaded and the V/Mo distribution is far from being equiprobable.

    3. You have free access to this content
      Inside Back Cover: Septulene: The Heptagonal Homologue of Kekulene (Angew. Chem. Int. Ed. 51/2012) (page 12897)

      Bharat Kumar, Ruth L. Viboh, Margel C. Bonifacio, William B. Thompson, Jonathan C. Buttrick, Babe C. Westlake, Min-Soo Kim, Prof. Robert W. Zoellner, Prof. Sergey A. Varganov, Philipp Mörschel, Jaroslav Teteruk, Prof. Dr. Martin U. Schmidt and Prof. Benjamin T. King

      Article first published online: 4 DEC 2012 | DOI: 10.1002/anie.201209345

      Thumbnail image of graphical abstract

      The seven-sided homologue of kekulene, septulene, has properties that are striking similar to kekulene. The Clar structures get it right by emphasizing the similarities between septulene and kekulene, but the Kekulé structures get it wrong by emphasizing the differences between septulene and kekulene. In their Communication on page 12 795 ff., B. King and co-workers describe the synthesis and properties of septulene, and discuss how this molecule serves to differentiate Clar and Kekulé structures.

    4. You have free access to this content
      Back Cover: A Sodium-Containing Quasicrystal: Using Gold To Enhance Sodium’s Covalency in Intermetallic Compounds (Angew. Chem. Int. Ed. 51/2012) (page 12898)

      Dr. Volodymyr Smetana, Dr. Qisheng Lin, Dr. Daniel K. Pratt, Dr. Andreas Kreyssig, Dr. Mehmet Ramazanoglu, Prof. John D. Corbett, Prof. Alan I. Goldman and Prof. Gordon J. Miller

      Article first published online: 5 DEC 2012 | DOI: 10.1002/anie.201209047

      Thumbnail image of graphical abstract

      A sodium-containing icosahedral quasicrystalline phase has been discovered. In their Communication page 12699 ff., G. J. Miller et al. describe the characterization of a Bergman-type i-Na13Au12Ga15 system. The existence and stability of this Na-containing icosahedral quasicrystal is tightly linked to its substantial Au content, which allows the electron-to-atom value to satisfy a Hume–Rothery stabilization rule, and creates novel Na–Au polar-covalent interactions.

  2. Editorial

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

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 51/2012 (pages 12635–12650)

      Article first published online: 10 DEC 2012 | DOI: 10.1002/anie.201290081

  4. News

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

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. Masahiro Miura (page 12656)

      Article first published online: 5 SEP 2012 | DOI: 10.1002/anie.201205931

      Thumbnail image of graphical abstract

      “Chemistry is fun because new findings raise my spirits. When I was eighteen I wanted to be either a mathematician or a chemist. …” This and more about Masahiro Miura can be found on page 12656.

  6. News

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

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. Isocyanide Chemistry. Applications in Synthesis and Material Science. Edited by Valentine G. Nenajdenko. (page 12659)

      Gian Cesare Tron

      Article first published online: 26 NOV 2012 | DOI: 10.1002/anie.201209150

      Thumbnail image of graphical abstract

      Wiley-VCH, Weinheim, 2012. 606 pp., hardcover, € 159.00.—ISBN 978-3527330430

  8. Highlight

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. CO2 Capture

      Enhancing Amine-Supported Materials for Ambient Air Capture (pages 12660–12661)

      Julian P. Sculley and Prof. Dr. Hong-Cai Zhou

      Article first published online: 19 NOV 2012 | DOI: 10.1002/anie.201207495

      Thumbnail image of graphical abstract

      Worth the wait: A new variable, zirconium content, has been added to the already complex amine-supported porous silica systems used for CO2 capture. SBA-15 incorporating Zr ions and loaded with poly(ethyleneimine) was exposed to simulated flue gas (10 % CO2) and ambient air (400 ppm CO2). Not only was the performance of the Zr-doped material significantly better than that of the pristine system, it also displayed improved desorption kinetics.

  9. Review

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

      Catalytic Asymmetric Dearomatization Reactions (pages 12662–12686)

      Chun-Xiang Zhuo, Prof. Dr. Wei Zhang and Prof. Dr. Shu-Li You

      Article first published online: 3 DEC 2012 | DOI: 10.1002/anie.201204822

      Thumbnail image of graphical abstract

      Breaking up the party: Arenes can be transformed efficiently into enantiomerically enriched, versatile ring systems by catalytic asymmetric dearomatization reactions. Known reaction types include oxidative dearomatization, dearomatization by Diels—Alder reactions, alkylative dearomatization of electron-rich arenes, transition-metal-catalyzed dearomatization reactions (see example), and cascade reaction sequences involving asymmetric dearomatization as the key step.

  10. Communications

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

      You have full text access to this OnlineOpen article
      Organized Plasmonic Clusters with High Coordination Number and Extraordinary Enhancement in Surface-Enhanced Raman Scattering (SERS) (pages 12688–12693)

      Dr. Nicolas Pazos-Perez, Dr. Claudia Simone Wagner, Dr. Jose M. Romo-Herrera, Prof. Luis M. Liz-Marzán, Prof.  F Javier García de Abajo, Prof. Alexander Wittemann, Prof. Andreas Fery and Prof. Ramón A. Alvarez-Puebla

      Article first published online: 4 NOV 2012 | DOI: 10.1002/anie.201207019

      Thumbnail image of graphical abstract

      Highly symmetric gold nanoparticle clusters with coordination numbers up to seven were produced by using coating with block copolymers. The resulting clusters were separated by density gradient centrifugation and characterized by using SEM and optical spectroscopy (see picture).

    2. DNA–Enzyme Conjugates

      Enhancement and Modulation of Enzymatic Activity through Higher-Order Structural Changes of Giant DNA–Protein Multibranch Conjugates (pages 12694–12698)

      Dr. Sergii Rudiuk, Anna Venancio-Marques and Prof. Damien Baigl

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201206962

      Thumbnail image of graphical abstract

      A giant DNA leap for enzyme-kind: Giant DNA–protein multibranch conjugates were shown to be composed of a single β-lactamase enzyme (green, see scheme) conjugated to up to four 48.5 kbp lambda phage DNA branches (blue lines). The conjugation of giant DNA induces a two- to fourfold enhancement of the enzymatic activity, which is modulated by changes in the higher-order DNA structure.

    3. Intermetallic Phases

      A Sodium-Containing Quasicrystal: Using Gold To Enhance Sodium’s Covalency in Intermetallic Compounds (pages 12699–12702)

      Dr. Volodymyr Smetana, Dr. Qisheng Lin, Dr. Daniel K. Pratt, Dr. Andreas Kreyssig, Dr. Mehmet Ramazanoglu, Prof. John D. Corbett, Prof. Alan I. Goldman and Prof. Gordon J. Miller

      Article first published online: 28 NOV 2012 | DOI: 10.1002/anie.201207076

      Thumbnail image of graphical abstract

      Golden opportunity: Na13Au12Ga15 is the first Na-containing, thermodynamically stable quasicrystal and was discovered during systematic exploration of the polar intermetallic Na–Au–Ga system. Its electron-to-atom ratio, 1.75, is extremely low for Bergman-type icosahedral phases, but it is the substantial Au content that allows Hume–Rothery stabilization and promotes novel Na–Au polar–covalent interactions, which stabilize the icosahedral phase.

    4. Water Splitting

      Molybdenum Boride and Carbide Catalyze Hydrogen Evolution in both Acidic and Basic Solutions (pages 12703–12706)

      Heron Vrubel and Prof. Dr. Xile Hu

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201207111

      Thumbnail image of graphical abstract

      Getting the hydrogen out: Molybdenum boride (MoB) and carbide (Mo2C) are excellent catalysts for electrochemical hydrogen evolution at both pH 0 and pH 14.

    5. Assay Development

      Quantifying Analytes in Paper-Based Microfluidic Devices Without Using External Electronic Readers (pages 12707–12710)

      Gregory G. Lewis, Matthew J. DiTucci and Prof. Scott T. Phillips

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201207239

      Thumbnail image of graphical abstract

      A matter of time: Two quantitative assays are presented that require only measurements of time and the ability to see and/or count to quantify the presence of a specific analyte. The strategies rely on specific changes in wetting properties of paper when a hydrophobic detection reagent (compound 1) reacts with a desired analyte to produce hydrophilic products. This change in wetting properties enables selective and quantitative detection of the analyte.

    6. Photosensitizers

      Highly Efficient Ultrafast Electron Injection from the Singlet MLCT Excited State of Copper(I) Diimine Complexes to TiO2 Nanoparticles (pages 12711–12715)

      Dr. Jier Huang, Onur Buyukcakir, Michael W. Mara, Dr. Ali Coskun, Dr. Nada M. Dimitrijevic, Gokhan Barin, Dr. Oleksandr Kokhan, Dr. Andrew B. Stickrath, Dr. Romain Ruppert, Dr. David M. Tiede, Prof. J. Fraser Stoddart, Prof. Jean-Pierre Sauvage and Prof. Lin X. Chen

      Article first published online: 8 NOV 2012 | DOI: 10.1002/anie.201204341

      Thumbnail image of graphical abstract

      Cu complexes as photosensitizers: Photoinduced charge-transfer dynamics from a copper(I) diimine complex to TiO2 nanoparticles were investigated by combining multiple time-resolved spectroscopic methods. An efficient and ultrafast electron transfer process from the singlet MLCT state was discovered as a result of structural control owing to the flattening of the tetrahedral geometry in the complex and the bulky groups in the ligands.

    7. Molecular Recognition

      Similar but Different: Thermodynamic and Structural Characterization of a Pair of Enantiomers Binding to Acetylcholinesterase (pages 12716–12720)

      Lotta Berg, Moritz S. Niemiec, Dr. Weixing Qian, Dr. C. David Andersson, Prof. Dr. Pernilla Wittung-Stafshede, Dr. Fredrik Ekström and Dr. Anna Linusson

      Article first published online: 19 NOV 2012 | DOI: 10.1002/anie.201205113

      Thumbnail image of graphical abstract

      Take a closer look: Unexpectedly, a pair of enantiomeric ligands proved to have similar binding affinities for acetylcholinesterase. Further studies indicated that the enantiomers exhibit different thermodynamic profiles. Analyses of the noncovalent interactions in the protein–ligand complexes revealed that these differences are partly due to nonclassical hydrogen bonds between the ligands and aromatic side chains of the protein.

    8. PET/NIR Imaging

      Aptamer-Functionalized, Ultra-Small, Monodisperse Silica Nanoconjugates for Targeted Dual-Modal Imaging of Lymph Nodes with Metastatic Tumors (pages 12721–12726)

      Li Tang, Dr. Xujuan Yang, Prof. Dr. Lawrence W. Dobrucki, Isthier Chaudhury, Qian Yin, Catherine Yao, Prof. Dr. Stéphane Lezmi, Prof. Dr. William G. Helferich, Prof. Dr. Timothy M. Fan and Prof. Dr. Jianjun Cheng

      Article first published online: 7 NOV 2012 | DOI: 10.1002/anie.201205271

      Thumbnail image of graphical abstract

      A dual-modal imaging probe based on size-controlled silica nanoconjugates was synthesized for targeted imaging of lymph nodes by means of both PET and near infrared fluorescence techniques. 20 nm nanoconjugates (see scheme) functionalized with an aptamer (green triangles) that targets 4T1 breast cancer cells improved the detection efficiency of sentinel lymph nodes with metastatic tumors.

    9. Porous Polymers

      Soluble Conjugated Microporous Polymers (pages 12727–12731)

      Dr. Ge Cheng, Dr. Tom Hasell, Dr. Abbie Trewin, Dr. Dave J. Adams and Prof. Andrew I. Cooper

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201205521

      Thumbnail image of graphical abstract

      Soluble and porous: Soluble conjugated microporous polymers (SCMPs) can be prepared by synthesizing discrete hyperbranched molecules. The materials can be cast from solution as thin films (see picture), suggesting a range of processing options that are not available for insoluble CMP networks. Soluble, conjugated dendrimers are porous and give insight into the structural origin of microporosity.

    10. CO2 Photoreduction

      Photocatalytic Conversion of Diluted CO2 into Light Hydrocarbons Using Periodically Modulated Multiwalled Nanotube Arrays (pages 12732–12735)

      Dr. Xiaojiang Zhang, Fei Han, Bo Shi, Samira Farsinezhad, Prof. Greg P. Dechaine and Prof. Karthik Shankar

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201205619

      Thumbnail image of graphical abstract

      Cu–Pt bimetallic shells supported on a double-walled TiO2 nanotube (PMTiNT) array are efficient photocatalysts for the room-temperature conversion of CO2 into light hydrocarbons, such as CH4, C2H4, and C2H6. When Cu0.33–Pt0.67/PMTiNT was used for the photoreduction of diluted CO2 (1 % in N2), an average hydrocarbon production rate of 3.7 mL g−1 h−1 or 6.1 mmol m−2 h−1 was realized under AM 1.5 one-sun illumination.

    11. Fluorescent Probes

      Oligothiophene Amphiphiles as Planarizable and Polarizable Fluorescent Membrane Probes (pages 12736–12739)

      Andrea Fin, Andreas Vargas Jentzsch, Dr. Naomi Sakai and Prof. Stefan Matile

      Article first published online: 4 NOV 2012 | DOI: 10.1002/anie.201206446

      Thumbnail image of graphical abstract

      Lessons from lobster coloration and the chemistry of vision suggested an approach to responsive fluorescent probes that can sense membrane potential, fluidity, and tension. Fluorophore deplanarization by lateral crowding along the scaffold (red circles) and fluorophore polarization by terminal donors (D), acceptors (A), and charges (+) are coupled to provide such membrane probes, as studies with unilamellar vesicles of phospholipids (DOPC, DPPC) show.

    12. Electrochemistry

      Electrodeposition of Crystalline and Photoactive Silicon Directly from Silicon Dioxide Nanoparticles in Molten CaCl2 (pages 12740–12744)

      Dr. Sung Ki Cho, Dr. Fu-Ren F. Fan and Prof. Allen J. Bard

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201206789

      Thumbnail image of graphical abstract

      Silicon for solar cells: Relatively pure, polycrystalline, and photoactive silicon was directly obtained from silicon dioxide nanoparticles (NP) by electrodeposition in molten CaCl2 salt on a silver electrode (see picture). This process is based on the formation of liquid droplets of a silver–silicon eutectic alloy and the continuous reduction of SiO2 to silicon. The deposited silicon shows a p-type behavior in photoelectrochemical measurements.

    13. Chiral Silanes

      Catalytic Enantioselective Synthesis of Alkenylhydrosilanes (pages 12745–12748)

      Dr. Kazunobu Igawa, Daisuke Yoshihiro, Nobumasa Ichikawa, Naoto Kokan and Prof. Dr. Katsuhiko Tomooka

      Article first published online: 7 NOV 2012 | DOI: 10.1002/anie.201207361

      Thumbnail image of graphical abstract

      Asymmetric silanes: A synthesis of nonracemic alkenylhydrosilanes has been developed based on the desymmetrization of a dihydrosilane through alkenylation with an alkyne using an asymmetric catalyst. The alkenylhydrosilane product can be used as a versatile chiral building block for other functionalized nonracemic silanes through the stereoselective conversion of its hydride and/or alkenyl moiety.

    14. Hybrid Materials

      Immobilization of a Molecular Cobaloxime Catalyst for Hydrogen Evolution on a Mesoporous Metal Oxide Electrode (pages 12749–12753)

      Dr. Nicoleta M. Muresan, Janina Willkomm, Dirk Mersch, Dr. Yana Vaynzof and Dr. Erwin Reisner

      Article first published online: 21 NOV 2012 | DOI: 10.1002/anie.201207448

      Thumbnail image of graphical abstract

      Energizing Cobalt on a 3D Electrode: An optically transparent mesoporous ITO film was derivatized with the novel proton reducing cobalt catalyst [Co]. The hybrid electrode showed high current densities, and spectroelectrochemical studies and extensive surface characterization demonstrate that the immobilized molecular catalyst remained intact on the electrode when applying a low potential.

    15. Polyoxometalates

      Directed Assembly of Inorganic Polyoxometalate-based Micrometer-Scale Tubular Architectures by Using Optical Control (pages 12754–12758)

      Dr. Geoffrey J. T. Cooper, Richard W. Bowman, E. Peter Magennis, Dr. Francisco Fernandez-Trillo, Prof. Cameron Alexander, Prof. Miles J. Padgett and Prof. Leroy Cronin

      Article first published online: 19 NOV 2012 | DOI: 10.1002/anie.201204405

      Thumbnail image of graphical abstract

      Go with the flow: Laser-induced flow patterns are used to direct the self-assembly of dissolved inorganic polyoxometalate clusters into robust, hollow tubular networks and micro-materials (see picture; scale bar: 500 μm) in real time. The hollow nature of these materials can be exploited to develop devices in which the self-assembled tubes act as microscopic flow channels.

    16. Assembly of a Gigantic Polyoxometalate Cluster {W200Co8O660} in a Networked Reactor System (pages 12759–12762)

      Andreu Ruiz de la Oliva, Dr. Victor Sans, Dr. Haralampos N. Miras, Dr. Jun Yan, Hongying Zang, Dr. Craig J. Richmond, Dr. De-Liang Long and Prof. Leroy Cronin

      Article first published online: 23 NOV 2012 | DOI: 10.1002/anie.201206572

      Thumbnail image of graphical abstract

      A giant leap: A networked reactor system was used for the first time for the discovery and synthesis of new polyoxometalates, including the gigantic title system (see picture; Co red, W blue). The system comprises of three reactors connected in a triangular array with a central triply connected reactor. This system was used to screen multiple one-pot reactions and reaction variables for the automated syntheses of polyoxometalates.

    17. Asymmetric Catalysis

      Chiral Copper(II)-Catalyzed Enantioselective Boron Conjugate Additions to α,β-Unsaturated Carbonyl Compounds in Water (pages 12763–12766)

      Prof. Dr. Shū Kobayashi, Pengyu Xu, Toshimitsu Endo, Dr. Masaharu Ueno and Taku Kitanosono

      Article first published online: 19 NOV 2012 | DOI: 10.1002/anie.201207343

      Thumbnail image of graphical abstract

      Copper pins on the boron: The enantioselective 1,4-addition of diboron to α,β-unsaturated compounds proceeds smoothly in the presence of catalytic amounts of Cu(OH)2 and chiral 2,2′-bipyridine ligand in water. A wide substrate scope of α,β-unsaturated carbonyl compounds, including acyclic, cyclic, and β,β-disubstituted enones, α,β-unsaturated esters, amides, and a nitrile, has been shown.

    18. Single-Molecule Magnets

      Coupling Dy3 Triangles to Maximize the Toroidal Moment (pages 12767–12771)

      Shuang-Yan Lin, Dr. Wolfgang Wernsdorfer, Dr. Liviu Ungur, Prof. Annie K. Powell, Yun-Nan Guo, Prof. Dr. Jinkui Tang, Dr. Lang Zhao, Prof. Liviu F. Chibotaru and Prof. Hong-Jie Zhang

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201206602

      Thumbnail image of graphical abstract

      A hexanuclear dysprosium(III) compound constructed by two Dy3 triangles in an edge-to-edge arrangement perfectly retains a nonmagnetic ground state and single-molecular-magnet behavior. Such an arrangement and the strong couplings over a μ4-O2− ion stabilize a similar arrangement of toroidal moments in the ground state, thus maximizing the toroidal moment of the complex. (Picture: Dy purple, C gray, N blue, O red.)

    19. Metal Ketimides

      Synthesis and Characterization of [M2(N[DOUBLE BOND]CtBu2)5] (M=Mn, Fe, Co): Metal Ketimide Complexes with Strong Metal–Metal Interactions (pages 12772–12775)

      Richard A. Lewis, Simona Morochnik, Alon Chapovetsky, Guang Wu and Prof. Trevor W. Hayton

      Article first published online: 7 NOV 2012 | DOI: 10.1002/anie.201206790

      Thumbnail image of graphical abstract

      Bond, metal–metal bond: Addition of 2.5 equiv of Li(N[DOUBLE BOND]CtBu2) to MCl2 (M=Mn, Fe, and Co), followed by addition of [12]crown-4, results in formation of [Li([12]crown-4)2][M2(N[DOUBLE BOND]CtBu2)5] in good yields. These complexes exhibit short M–M distances and strong magnetic communication between metal centers, thus demonstrating that ketimides are viable co-ligands for promoting metal–metal bonding.

    20. Cyclophanes

      A Polymacrocyclic Oligoarylamine with a Pseudobeltane Motif: Towards a Cylindrical Multispin System (pages 12776–12781)

      Daisuke Sakamaki, Dr. Akihiro Ito, Dr. Ko Furukawa, Prof. Dr. Tatsuhisa Kato, Dr. Motoo Shiro and Prof. Dr. Kazuyoshi Tanaka

      Article first published online: 20 NOV 2012 | DOI: 10.1002/anie.201206831

      Thumbnail image of graphical abstract

      Spin doctor: The polymacrocyclic oligoarylamine in the picture serves as a multispin source owing to its multi-electron redox activity. As a result of its pseudobeltane structure and para-phenylenediamine bridges, the radical cation can convert between two sideslipped structures with a windshield-wiper-like motion. In contrast, the tetraazacyclophane units are rigid components in the polymacrocycle.

    21. Electron Transfer

      Self-Assembled Bilayer Films of Ruthenium(II)/Polypyridyl Complexes through Layer-by-Layer Deposition on Nanostructured Metal Oxides (pages 12782–12785)

      Dr. Kenneth Hanson, Daniel A. Torelli, Dr. Aaron K. Vannucci, Dr. M. Kyle Brennaman, Hanlin Luo, Dr. Leila Alibabaei, Dr. Wenjing Song, Dennis L. Ashford, Michael R. Norris, Dr. Christopher R. K. Glasson, Dr. Javier J. Concepcion and Prof. Thomas J. Meyer

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201206882

      Thumbnail image of graphical abstract

      Simple assembly: A “layer-by-layer” deposition of functionalized dyes/catalysts on the surfaces of nanocrystalline oxides is introduced. The strategy is general and offers considerable flexibility based on phosphonate- or carboxylate-binding groups with ZrIV as bridging ions. The resulting bilayer structures are capable of supporting rapid intra-layer energy and electron transfer (see picture).

    22. Peptide Catalysis

      Construction of an All-Carbon Quaternary Stereocenter by the Peptide-Catalyzed Asymmetric Michael Addition of Nitromethane to β-Disubstituted α,β-Unsaturated Aldehydes (pages 12786–12789)

      Dr. Kengo Akagawa and Prof. Dr. Kazuaki Kudo

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201206916

      Thumbnail image of graphical abstract

      Pepping up Michael: An asymmetric Michael addition of nitromethane to β-disubstituted α,β-unsaturated aldehydes was realized by a resin-supported peptide catalyst. Whereas the use of a low-molecular-weight catalyst resulted in poor yields, the peptide effectively promoted the reaction in aqueous media with high enantioselectivity.

    23. Dehydrogenation

      Cooperative Catalysis by Iridium Complexes with a Bipyridonate Ligand: Versatile Dehydrogenative Oxidation of Alcohols and Reversible Dehydrogenation–Hydrogenation between 2-Propanol and Acetone (pages 12790–12794)

      Ryoko Kawahara, Dr. Ken-ichi Fujita and Prof. Dr. Ryohei Yamaguchi

      Article first published online: 7 NOV 2012 | DOI: 10.1002/anie.201206987

      Thumbnail image of graphical abstract

      Going into reverse: An efficient and versatile catalytic system for the dehydrogenative oxidation of alcohols under extremely mild conditions has been developed using a Cp*Ir complex with bipyridonate ligand as catalyst (see scheme, Cp*=pentamethylcyclopentadienyl). Reversible and repetitive transformation between 2-propanol and acetone by catalytic dehydrogenation–hydrogenation is also achieved.

    24. Kekulene

      Septulene: The Heptagonal Homologue of Kekulene (pages 12795–12800)

      Bharat Kumar, Ruth L. Viboh, Margel C. Bonifacio, William B. Thompson, Jonathan C. Buttrick, Babe C. Westlake, Min-Soo Kim, Prof. Robert W. Zoellner, Prof. Sergey A. Varganov, Philipp Mörschel, Jaroslav Teteruk, Prof. Dr. Martin U. Schmidt and Prof. Benjamin T. King

      Article first published online: 12 OCT 2012 | DOI: 10.1002/anie.201203266

      Thumbnail image of graphical abstract

      A family likeness: The seven-sided homologue of kekulene, septulene (see structure), has been synthesized in seven steps by ring-closing metathesis. Its properties (spectroscopic and structural) are strikingly similar to those of kekulene despite its sevenfold symmetry and resulting non-alternant structure. The chair-type conformation in the crystal arises from packing forces. Septulene is probably a free pseudorotor in the gas phase.

    25. Porphyrinoids

      A 20π-Electron Heteroporphyrin Containing a Thienopyrrole Unit (pages 12801–12805)

      Yi Chang, Huachao Chen, Zhikuan Zhou, Yue Zhang, Christian Schütt, Prof. Rainer Herges and Prof. Zhen Shen

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201204954

      Thumbnail image of graphical abstract

      Easy as π: A stable nonaromatic heteroporphyrin bearing a thienopyrrole moiety has been prepared. The nonaromatic nature of this compound is clearly evident based on UV/Vis absorption, 1H NMR spectroscopy, and theoretical calculations. Single-crystal X-ray analysis demonstrates that the molecule adopts a planar conformation with clear alternation in the C[BOND]C bond lengths around the periphery of the macrocycle.

    26. Water–Solid Interfaces

      Acidic Water Monolayer on Ruthenium(0001) (pages 12806–12809)

      Youngsoon Kim, Dr. Eui-seong Moon, Sunghwan Shin and Prof. Heon Kang

      Article first published online: 8 NOV 2012 | DOI: 10.1002/anie.201205756

      Thumbnail image of graphical abstract

      Acidic water: The first monolayer of water on a Ru(0001) surface is anomalously acidic compared to bulk water, according to infrared and mass spectroscopic investigations of the water layer using ammonia as a probe for surface acidity. The observation suggests that acid–base chemistry may be quite different at the water–metal interfaces than in aqueous solution.

    27. Computational Electrochemistry

      Construction of Pourbaix Diagrams for Ruthenium-Based Water-Oxidation Catalysts by Density Functional Theory (pages 12810–12814)

      Aleksandr V. Marenich, Abir Majumdar, Michelle Lenz, Prof. Christopher J. Cramer and Prof. Donald G. Truhlar

      Article first published online: 19 NOV 2012 | DOI: 10.1002/anie.201206012

      Thumbnail image of graphical abstract

      We can do better! The new density functionals M11-L and M11 and the SMD implicit solvation model were used to predict reduction potential–pH equilibrium diagrams (see example) for two ruthenium-based water-oxidation catalysts and their derivatives in aqueous solution. The observed improved accuracy for transition-metal complexes opens new opportunities for the use of theory in the understanding and design of catalysts containing transition metals.

    28. Synthetic Methods

      Direct Copper-Catalyzed α-Arylation of Benzyl Phenyl Ketones with Aryl Iodides: Route towards Tamoxifen (pages 12815–12819)

      Dr. Grégory Danoun, Dr. Anis Tlili, Dr. Florian Monnier and Dr. Marc Taillefer

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201206024

      Thumbnail image of graphical abstract

      No activation needed: The first efficient method for direct α-arylation of non-activated or non-protected family of enolizable ketones with simple aryl iodides employs a catalytic copper system. The method shows potential for the easy and step-economical synthesis of tamoxifen, the most commonly administrated drug for the management of breast cancer. R, R′, R′′ = electron-donating or electron-withdrawing groups.

    29. Fast Photoswitches

      Fastest Thermal Isomerization of an Azobenzene for Nanosecond Photoswitching Applications under Physiological Conditions (pages 12820–12823)

      Dr. Jaume Garcia-Amorós, Mireia Díaz-Lobo, Prof. Dr. Santi Nonell and Prof. Dr. Dolores Velasco

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201207602

      Thumbnail image of graphical abstract

      When speed is of the essence: After photoisomerization to its metastable cis form, an azo dye must undergo fast thermal isomerization back to the trans form to be suitable for real-time information transmission. The azopyrimidine shown has a relaxation time (τ) of just 40 ns under physiological conditions, as well as high biocompatibility, as determined by Escherichia coli growth in its presence (see picture).

    30. CO2 Hydrosilylation

      Effective Fixation of CO2 by Iridium-Catalyzed Hydrosilylation (pages 12824–12827)

      Dr. Ralte Lalrempuia, Dr. Manuel Iglesias, Dr. Victor Polo, Dr. Pablo J. Sanz Miguel, Dr. Francisco J. Fernández-Alvarez, Prof. Jesús J. Pérez-Torrente and Prof. Luis A. Oro

      Article first published online: 14 SEP 2012 | DOI: 10.1002/anie.201206165

      Thumbnail image of graphical abstract

      CO2 as feedstock: An air- and moisture-stable iridium(III) catalyst effectively promotes the hydrosilylation of CO2. This reaction leads to silyl formate in a highly selective manner and proceeds efficiently under mild conditions, most likely by an outer-sphere mechanism, as suggested by theoretical calculations.

    31. C[BOND]H Alkylation

      Regioselective C[BOND]H Alkylation of Anisoles with Olefins Catalyzed by Cationic Half-Sandwich Rare Earth Alkyl Complexes (pages 12828–12832)

      Dr. Juzo Oyamada and Prof. Dr. Zhaomin Hou

      Article first published online: 7 NOV 2012 | DOI: 10.1002/anie.201206233

      Thumbnail image of graphical abstract

      A half sandwich helping: Cationic rare-earth alkyl species generated from half-sandwich rare-earth dialkyl complexes and [Ph3C][B(C6F5)4] can serve as unique catalysts for the C[BOND]H regioselective alkylation of anisoles with alkenes. The reaction affords either ortho-monoalkylated derivatives or products substituted at the benzylic position, depending on the substrate chosen.

    32. Natural Product Synthesis

      Total Synthesis of the Tremorgenic Indole Diterpene Paspalinine (pages 12833–12836)

      Dr. Masaru Enomoto, Dr. Akira Morita and Prof. Dr. Shigefumi Kuwahara

      Article first published online: 7 NOV 2012 | DOI: 10.1002/anie.201206299

      Thumbnail image of graphical abstract

      Succinct and stereoselective: A high-yielding two-step indole ring installation comprising the Stille cross-coupling and a PdII-mediated oxidative heterocyclization was exploited in a concise total synthesis of paspalinine. The trans-anti-trans CDE fused ring system of the heptacyclic natural product was established highly stereoselectively through hydroxy-directed cyclopropanation and allylic selenoxide rearrangement.

    33. Heterobiaryl Cross-Coupling

      Highly Reactive, Single-Component Nickel Catalyst Precursor for Suzuki–Miyuara Cross-Coupling of Heteroaryl Boronic Acids with Heteroaryl Halides (pages 12837–12841)

      Dr. Shaozhong Ge and Prof. John F. Hartwig

      Article first published online: 7 NOV 2012 | DOI: 10.1002/anie.201207428

      Thumbnail image of graphical abstract

      One for all: The coupling of a range of nitrogen- and sulfur-containing heteroaryl halides with five-membered nitrogen-, oxygen-, and sulfur-containing heteroaryl boronic acids were achieved in high yields with only 0.5 mol % of the single-component nickel precatalyst [(dppf)NiCl(cinnamyl)] (dppf=1,1′-bis(diphenylphosphanyl)ferrocene). The reaction demonstrates good functional group compatibility, and is easily conducted on a large scale without a dry box.

    34. C[BOND]H Activation

      Palladium(0)-Catalyzed Enantioselective C[BOND]H Arylation of Cyclopropanes: Efficient Access to Functionalized Tetrahydroquinolines (pages 12842–12845)

      Tanguy Saget and Prof. Dr. Nicolai Cramer

      Article first published online: 19 NOV 2012 | DOI: 10.1002/anie.201207959

      Thumbnail image of graphical abstract

      Activated: The title reaction proceeds efficiently with 1 mol % of palladium and gives tetrahydroquinolines in excellent enantioselectivities (see scheme). The enantiodiscriminating concerted metalation–deprotonation step occurs via a rare seven-membered palladacycle. The cyclopropyl-substituted tetrahydroquinolines can be regioselectively and enantiospecifically reduced to chiral tetrahydrobenzoazepines.

    35. Natural Product Synthesis

      Total Synthesis of the Unusual Monoterpenoid Indole Alkaloid (±)-Alstilobanine A (pages 12846–12849)

      Yiqing Feng, Max M. Majireck and Prof. Dr. Steven M. Weinreb

      Article first published online: 19 NOV 2012 | DOI: 10.1002/anie.201207949

      Thumbnail image of graphical abstract

      Tetracyclic monoterpene alkaloid alstilobanine A was obtained in racemic form. The pivotal steps of the total synthesis are a novel conjugate addition of an ester enolate with a nitrosoalkene, as well as a formal [2+2] intramolecular cycloaddition leading to a β-lactone to generate the requisite cis-fused 2-azadecalin moiety of the alkaloid. TMSE=trimethylsilylethoxy, Ts=4-toluenesulfonyl.

    36. Natural Product

      Stereocontrolled Total Synthesis of (+)-UCS1025A (pages 12850–12853)

      Dr. Kenji Uchida, Takahiro Ogawa, Yoshinori Yasuda, Hiraku Mimura, Dr. Teppei Fujimoto, Prof. Dr. Tohru Fukuyama, Dr. Toshiyuki Wakimoto, Dr. Tomohiro Asakawa, Dr. Yoshitaka Hamashima and Prof. Dr. Toshiyuki Kan

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201207800

      Thumbnail image of graphical abstract

      Under control: A stereocontrolled total synthesis of (+)-UCS1025A, a potent telomerase inhibitor, was achieved. The synthesis features an intramolecular Diels–Alder reaction, a tandem Staudinger/aza-Wittig reaction, and stereoselective construction of the hemiaminal moiety facilitated by neighboring-group participation.

    37. Multicomponent Oxide Catalysts

      Vanadium Distribution in Four-Component Mo-V-Te-Nb Mixed-Oxide Catalysts from First Principles: How to Explore the Numerous Configurations? (pages 12854–12858)

      Gang Fu, Xin Xu and Philippe Sautet

      Article first published online: 21 NOV 2012 | DOI: 10.1002/anie.201207638

      Thumbnail image of graphical abstract

      A V V good idea: The V occupancy (shown as a scale of green in the picture) and V–V pair probability in a Mo-V-Te-Nb mixed oxide were determined by weighted average over all possible (up to 8000) configurations on the basis of estimated DFT energies, which agreed well with those obtained by full optimization (R2>0.94, maximum error below 0.05 eV). This rapid approach provided insight into the origin of the catalytic activity of these solids.

    38. Halogen Azides

      A Comparison of the Solid-State Structures of Halogen Azides XN3 (X=Cl, Br, I) (pages 12859–12863)

      Benjamin Lyhs, Dieter Bläser, Dr. Christoph Wölper, Prof. Stephan Schulz and Prof. Georg Jansen

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201206028

      Thumbnail image of graphical abstract

      Delicate crystals: ClN3 adopts a polymeric structure in the solid state (see picture; N blue, Cl green) with short intermolecular Cl⋅⋅⋅Cl distances, as was observed for the elemental halogen.

    39. Organocatalysis

      Asymmetric Brønsted Acid Catalyzed Cycloadditions—Efficient Enantioselective Synthesis of Pyrazolidines, Pyrazolines, and 1,3-Diamines from N-Acyl Hyrazones and Alkenes (pages 12864–12868)

      Prof. Dr. Magnus Rueping, Modhu Sudan Maji, Hatice Başpınar Küçük and Iuliana Atodiresei

      Article first published online: 19 NOV 2012 | DOI: 10.1002/anie.201205813

      Thumbnail image of graphical abstract

      A general, metal-free, highly enantioselective Brønsted acid catalyzed [3+2] cycloaddition between hydrazones and alkenes has been developed that affords pyrazolidine derivatives (see scheme). The resulting optically active pyrazolidines can undergo many chemical transformations which allow, for example, the enantioselective synthesis of valuable pyrazolines and 1,3-diamines.

    40. Coordination Chemistry

      Side-On Coordinated Distannene: An Unprecedented Nickel(0) Complex (pages 12869–12873)

      Jens Henning and Prof. Dr. Lars Wesemann

      Article first published online: 19 NOV 2012 | DOI: 10.1002/anie.201206767

      Thumbnail image of graphical abstract

      η2-coordination of a Sn[BOND]Sn bond: An intramolecular distannene was synthesized in a straightforward fashion from 4,5-dilithio-9,9-dimethylxanthene. This compound reacts with [Ni(cod)2] to form a Ni0 complex with an unprecedented Sn2Ni triangle (see scheme; cod=1,5-cyclooctadiene).

    41. Glycophospholipid Monolayers

      Subgel Phase Structure in Monolayers of Glycosylphosphatidylinositol Glycolipids (pages 12874–12878)

      Dr. Cristina Stefaniu, Dr. Ivan Vilotijevic, Dr. Mark Santer, Dr. Daniel Varón Silva, Prof. Dr. Gerald Brezesinski and Prof. Dr. Peter H. Seeberger

      Article first published online: 7 NOV 2012 | DOI: 10.1002/anie.201205825

      Thumbnail image of graphical abstract

      Heads and tails: GPI glycolipid monolayers on the air/liquid interface are characterized by the ordering of entire molecules, as observed by grazing-incidence X-ray diffraction. Strong hydrogen bonding interactions are responsible for ordering of the head groups to form supercells. These forces are likely to be the key to the interactions of GPI-anchored proteins and/or GPIs in cell membranes.

    42. Enzyme Mechanisms

      Switching between O- and C-Glycosyltransferase through Exchange of Active-Site Motifs (pages 12879–12883)

      Alexander Gutmann and Prof. Dr. Bernd Nidetzky

      Article first published online: 14 NOV 2012 | DOI: 10.1002/anie.201206141

      Thumbnail image of graphical abstract

      Mechanistic implications: Distinct active-site motifs in plant aryl glucosyltransferases of the GT-1 family differentiate between C- and O-glycosylation activity on a phloretin acceptor. In the implicated protein design principle the exchange of active-site motifs results in reversible switch between C/O-glycoside specificity. The proposed mechanism of the C-glycosyltransferase involves direct nucleophilic displacement at the anomeric carbon.

    43. Bowl-Shaped Molecules

      Tribenzotriquinacene: A Versatile Synthesis and C3-Chiral Platforms (pages 12884–12887)

      Georgios Markopoulos, Lars Henneicke, Prof. Jun Shen, Prof. Yoshio Okamoto, Prof. Peter G. Jones and Prof. Henning Hopf

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201207220

      Thumbnail image of graphical abstract

      Fusing rings: A new synthesis of the bowl-shaped hydrocarbon tribenzotriquinacene is presented (see scheme). The synthesis allows easy access to ortho-functionalized and C3-chiral derivatives that are attractive for supramolecular chemistry and asymmetric catalysis.

    44. NMR Spectroscopy

      A Homonuclear Rotational Echo Double-Resonance Method for Measuring Site-Resolved Distance Distributions in I=1/2 Spin Pairs, Clusters, and Multispin Systems (pages 12888–12891)

      Dr. Jinjun Ren and Prof. Dr. Hellmut Eckert

      Article first published online: 19 NOV 2012 | DOI: 10.1002/anie.201207094

      Thumbnail image of graphical abstract

      In a new solid-state NMR method a double-quantum Hamiltonian based on a POST-C7 pulse sequence is used to recouple the homonuclear dipole–dipole interactions. Similar to the heteronuclear rotational echo double-resonance (REDOR) method, an analysis of the difference signal at short evolution times yields site-resolved summed squares of the dipole–dipole coupling constants.

    45. Ordered Carbides

      Access to Ordered Porous Molybdenum Oxycarbide/Carbon Nanocomposites (pages 12892–12896)

      Thomas Lunkenbein, Dr. Dirk Rosenthal, Torsten Otremba, Dr. Frank Girgsdies, Zihui Li, Hiroaki Sai, Carina Bojer, Dr. Gudrun Auffermann, Prof. Dr. Ulrich Wiesner and Prof. Dr. Josef Breu

      Article first published online: 9 NOV 2012 | DOI: 10.1002/anie.201206183

      Thumbnail image of graphical abstract

      Hexagonally ordered mesoporous molybdenum oxycarbide/carbon (MoC/C) nanocomposites were directly accessed by heat treatment of mesostructured poly(butadiene-block-2-vinylpyridine) (PB-b-P2VP) and molybdophosphoric acid. PB-b-P2VP serves as structure-directing agent and as carbon source. The high specific surface area obtained for the nanocomposites renders the materials interesting for potential applications, such as in the catalytic decomposition of NH3.

SEARCH

SEARCH BY CITATION