Angewandte Chemie International Edition

Cover image for Angewandte Chemie International Edition

February 25, 2013

Volume 52, Issue 9

Pages 2375–2610

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    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: A Hydrogen-Bond Flip-Flop through a Bjerrum-Type Defect (Angew. Chem. Int. Ed. 9/2013) (page 2375)

      Martin Olschewski, Dr. Jörg Lindner and Prof. Dr. Peter Vöhringer

      Article first published online: 1 FEB 2013 | DOI: 10.1002/anie.201300349

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      Hydrogen bonds can dynamically reverse their direction by means of an ultrafast flip-flop motion of the donor and acceptor moieties engaged in the noncovalent contact. In their Communication on page 2602 ff., P. Vöhringer and co-workers describe an application of femtosecond two-dimensional infrared exchange spectroscopy (2DIR-EXSY) in which these elementary dynamics are observed in the time domain of a simple model system, a vicinal diol.

    2. You have free access to this content
      Inside Cover: Access to Organometallic Arylcobaltcorrins through Radical Synthesis: 4-Ethylphenylcobalamin, a Potential “Antivitamin B12” (Angew. Chem. Int. Ed. 9/2013) (page 2376)

      Mag. Markus Ruetz, Dr. Carmen Gherasim, Prof. Dr. Karl Gruber, Dr. Sergey Fedosov, Prof. Dr. Ruma Banerjee and Prof. Dr. Bernhard Kräutler

      Article first published online: 1 FEB 2013 | DOI: 10.1002/anie.201300393

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      An organometallic arylcobalamin is a “locked” form of vitamin B12 or “antivitamin B12”, and is accessible by a radical reaction, as reported by B. Kräutler et al. in their Communication on page 2606 ff. “Antivitamins B12” are novel molecular tools to induce functional vitamin B12 deficiency in laboratory animals. These studies may be helpful in clarifying controversial questions dealing with irreparable damage in the central and peripheral nervous system that is associated with vitamin B12 deficiency in humans.

    3. You have free access to this content
      Inside Back Cover: Selectivity of CO2 Reduction on Copper Electrodes: The Role of the Kinetics of Elementary Steps (Angew. Chem. Int. Ed. 9/2013) (page 2611)

      Dr. Xiaowa Nie, Monica R. Esopi, Prof. Michael J. Janik and Prof. Aravind Asthagiri

      Article first published online: 10 FEB 2013 | DOI: 10.1002/anie.201300342

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      CO2 electroreduction on copper is described by M. J. Janik, A. Asthagiri, and co-workers in their Communication on page 2459 ff. DFT calculations (incorporating the role of water solvation) of the activation barriers of elementary steps reveal a new path: Instead of proceeding through a CHO intermediate (which leads to methanol), methane formation goes through reduction of CO to COH, which eventually leads to CHx species that can produce both methane and ethylene, as observed experimentally.

    4. You have free access to this content
      Back Cover: A Structured Monodisperse PEG for the Effective Suppression of Protein Aggregation (Angew. Chem. Int. Ed. 9/2013) (page 2612)

      Dr. Takahiro Muraoka, Kota Adachi, Dr. Mihoko Ui, Shunichi Kawasaki, Dr. Nabanita Sadhukhan, Haruki Obara, Dr. Hidehito Tochio, Prof. Masahiro Shirakawa and Prof. Kazushi Kinbara

      Article first published online: 1 FEB 2013 | DOI: 10.1002/anie.201300347

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      Poly(ethylene glycol) (PEG) with a discrete triangular structure exhibits hydrophilicity/hydrophobicity switching at a lower temperature than the corresponding linear PEG. In their Communication on page 2430 ff, T. Muraoka, K. Kinbara, and co-workers report that such a triangular PEG analogue helps lysozyme preserve the higher order structure at high temperatures and efficiently suppresses its thermal aggregation.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 9/2013 (pages 2379–2392)

      Article first published online: 19 FEB 2013 | DOI: 10.1002/anie.201390006

  3. Flashback

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. 50 Years Ago ... (page 2390)

      Article first published online: 19 FEB 2013 | DOI: 10.1002/anie.201300263

      Angewandte Chemie International Edition was first published in 1962, the mother journal first in 1888. In this monthly flashback, we feature some of the articles that appeared 50 years ago. This look back can open our eyes, stimulate discussion, or even raise a smile.

  4. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    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. Flashback
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Dayang Wang (page 2400)

      Article first published online: 22 OCT 2012 | DOI: 10.1002/anie.201207558

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      “My motto is ‘science lies in simplicity’. I am waiting for the day when someone will discover a microscope to visualize water, ions, and gases …” This and more about Dayang Wang can be found on page 2400.

  6. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Flashback
    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. Flashback
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Aromaticity and Other Conjugation Effects. By Rolf Gleiter and Gebhard Haberhauer. (pages 2403–2404)

      Lawrence T. Scott, Hee Yeon Cho, Maria N. Eliseeva, Edward A. Jackson, Takayuki Tanaka and Tomoharu Tanikawa

      Article first published online: 30 JAN 2013 | DOI: 10.1002/anie.201209331

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      Wiley-VCH, Weinheim, 2012. 452 pp., hardcover, € 129.00.—ISBN 978-3527329465 (softcover, € 59.00.—ISBN 978-3527329342)

  8. Highlights

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

      How Bacteria Choose Phosphate (pages 2406–2407)

      Prof. Dr. Roger S. Goody

      Article first published online: 16 JAN 2013 | DOI: 10.1002/anie.201209376

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      Discriminating against arsenate: Determination of the structure of periplasmic phosphate binding proteins at very high resolution provides the basis for understanding the high discrimination of bacteria against arsenate. The results complete our insight into earlier erroneous conclusions on the ability of certain bacteria to use arsenate instead of phosphate.

    2. Fluorescent Labeling

      The Power of Fluorogenic Probes (pages 2408–2410)

      Dr. André Nadler and Priv.-Doz. Dr. Carsten Schultz

      Article first published online: 21 JAN 2013 | DOI: 10.1002/anie.201209733

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      A definite turn-on: Turning on fluorescence only where successful labeling is happening sounds as desirable as delivering a drug only where the drug target resides. New fluorogenic xanthene derivatives from the Bertozzi research group are getting us closer to “magic bullet” dyes (see picture).

  9. Review

    1. Top of page
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    4. Flashback
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    7. News
    8. Book Review
    9. Highlights
    10. Review
    11. Communications
    1. Nanostructures

      Engineering Hierarchical Nanostructures by Elastocapillary Self-Assembly (pages 2412–2425)

      Dr. Michaël De Volder and Prof. A. John Hart

      Article first published online: 21 JAN 2013 | DOI: 10.1002/anie.201205944

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      New insights in capillary interactions between nanofilaments have led to versatile and scalable methods to build complex structures that cannot be achieved by any other processing technique. Understanding the control of this process is conducive to the development of high-performance battery and capacitor electrodes as well as photovoltaics, electrical interconnects, and other smart materials.

  10. Communications

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

      Radio-Frequency Ionization of Organic Compounds for Mass Spectrometry Analysis (pages 2426–2429)

      Behrooz Zekavat and Prof. Touradj Solouki

      Article first published online: 31 JAN 2013 | DOI: 10.1002/anie.201208717

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      A new ionization technique: A radio-frequency signal was used to ionize neutral organic molecules in the ultrahigh-vacuum region of a Fourier transform ion cyclotron resonance mass spectrometer. Radio-frequency ionization (RFI) yielded signal/noise (S/N) ratios roughly six times higher than those generated by conventional 70 eV electron impact ionization (EI).

    2. Protein Manipulation

      A Structured Monodisperse PEG for the Effective Suppression of Protein Aggregation (pages 2430–2434)

      Dr. Takahiro Muraoka, Kota Adachi, Dr. Mihoko Ui, Shunichi Kawasaki, Dr. Nabanita Sadhukhan, Haruki Obara, Dr. Hidehito Tochio, Prof. Masahiro Shirakawa and Prof. Kazushi Kinbara

      Article first published online: 30 JAN 2013 | DOI: 10.1002/anie.201206563

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      Part of the solution: A PEG with a discrete triangular structure exhibits hydrophilicity/hydrophobicity switching upon increasing temperatures, and suppresses the thermal aggregation of lysozyme to retain nearly 80 % of the enzymatic activity. CD and NMR spectroscopic studies revealed that, with the structured PEG, the higher-order structures of lysozyme persist at high temperature, and the native conformation is recovered after cooling.

    3. Photocatalysis

      Triazine-based Carbon Nitrides for Visible-Light-Driven Hydrogen Evolution (pages 2435–2439)

      Katharina Schwinghammer, Brian Tuffy, Maria B. Mesch, Eva Wirnhier, Charlotte Martineau, Prof. Francis Taulelle, Prof. Wolfgang Schnick, Prof. Jürgen Senker and Prof. Bettina V. Lotsch

      Article first published online: 22 JAN 2013 | DOI: 10.1002/anie.201206817

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      A new dimension: The doping of amorphous poly(triazine imide) (PTI) through ionothermal copolymerization of dicyandiamide with 4-amino-2,6-dihydroxypyrimidine (4AP) results in triazine-based carbon nitrides with increased photoactivity for water splitting compared to crystalline poly(triazine imide) (PTI/Li+Cl, see picture) and melon-type carbon nitrides. This family of carbon nitride semiconductors has potential as low-cost, environmentally clean photocatalysts for solar fuel production.

    4. Hydrogen Exchange

      Rapid Characterization of Hydrogen Exchange in Proteins (pages 2440–2443)

      Anushikha Thakur, Dr. Kousik Chandra, Abhinav Dubey, Dr. Patrick D'Silva and Prof. Hanudatta S. Atreya

      Article first published online: 22 JAN 2013 | DOI: 10.1002/anie.201206828

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      Kinetics and thermodynamics of amide hydrogen exchange in proteins can be investigated with two-dimensional 13CO–15N NMR correlation experiments (see picture). The spectra are acquired with high resolution and sensitivity. A single type of experiment on one sample serves to characterize hydrogen–deuterium fractionation factors and hydrogen-exchange rates that span three orders of magnitude.

    5. Gold Chemistry

      Activation of Multiple C[BOND]H Bonds Promoted by Gold in AuNbO3+ Clusters (pages 2444–2448)

      Dr. Xiao-Nan Wu, Dr. Xiao-Na Li, Dr. Xun-Lei Ding and Prof. Dr. Sheng-Gui He

      Article first published online: 25 JAN 2013 | DOI: 10.1002/anie.201207016

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      Single, double, triple: Highly selective double H atom abstraction (HAA) from ethane and triple HAA from n-butane by AuNbO3+ clusters have been characterized by mass spectrometry and DFT calculations. The multiple HAAs are initiated by oxygen-centered radicals and promoted by gold. The gold atoms act as electron acceptors during the triple HAAs and help to store a pair of valence electrons between Au and Nb atoms (see picture).

    6. Molecular Electronics

      Tactile-Feedback Stabilized Molecular Junctions for the Measurement of Molecular Conductance (pages 2449–2453)

      Prof. I-Wen Peter Chen, Dr. Wei-Hsiang Tseng, Mong-Wen Gu, Dr. Li-Chen Su, Chan-Hsian Hsu, Wei-Hsuan Chang and Prof. Chun-hsien Chen

      Article first published online: 22 JAN 2013 | DOI: 10.1002/anie.201207116

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      Handling the (AFM) tip: The duration of stable molecular junctions was prolonged using a tactile feedback method in which the operator can sense the force of the AFM tip on the sample surface (see picture). The movement of the tip is adjusted accordingly, maintaining a more consistent current (i) and voltage (V), instead of having the tip move at a constant preset speed, as in the conventional setup.

    7. Electrodeposition

      Structural Accelerating Effect of Chloride on Copper Electrodeposition (pages 2454–2458)

      Yuriy I. Yanson and Dr. Marcel J. Rost

      Article first published online: 23 JAN 2013 | DOI: 10.1002/anie.201207342

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      Under the microscope: In situ, video-rate scanning-tunneling-microscopy imaging during Cu electrodeposition reveals a profound structural accelerating effect of Cl on the deposition process (see images). This effect could be present in systems with different metals and different additives. The structural accelerating effect is important for the fundamental understanding of electrodeposition phenomena and for applications in industry.

    8. Electroreduction

      Selectivity of CO2 Reduction on Copper Electrodes: The Role of the Kinetics of Elementary Steps (pages 2459–2462)

      Dr. Xiaowa Nie, Monica R. Esopi, Prof. Michael J. Janik and Prof. Aravind Asthagiri

      Article first published online: 23 JAN 2013 | DOI: 10.1002/anie.201208320

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      On the right path: Based on DFT calculations (incorporating the role of water solvation) of the activation barriers of elementary steps, a new path that leads to methane and ethylene for CO2 electroreduction on Cu(111) was identified. Methane formation proceeds through reduction of CO to COH (path II, see picture), which leads to CHx species that can produce both methane and ethylene, as observed experimentally.

    9. Giant Vesicles

      Hydrodynamically Driven Self-Assembly of Giant Vesicles of Metal Nanoparticles for Remote-Controlled Release (pages 2463–2468)

      Dr. Jie He, Zengjiang Wei, Lei Wang, Zuleykhan Tomova, Taarika Babu, Prof. Dr. Chaoyang Wang, Prof. Dr. Xiaojun Han, Prof. Dr. John T. Fourkas and Prof. Dr. Zhihong Nie

      Article first published online: 30 JAN 2013 | DOI: 10.1002/anie.201208425

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      The hydrodynamics of laminar flow in a microfluidic device has been used to control the continuous self-assembly of gold nanoparticles (NPs) tethered with amphiphilic block copolymers. Spherical micelles, giant vesicles (500 nm–2.0 μm), or disk-like micelles could be formed by varying the flow rates of fluids. Such vesicles can release encapsulated hydrophilic species by using near-IR light (see picture).

    10. Asymmetric Synthesis

      Regio- and Enantioselective Aminofluorination of Alkenes (pages 2469–2473)

      Dr. Wangqing Kong, Pascal Feige, Teresa de Haro and Prof. Dr. Cristina Nevado

      Article first published online: 30 JAN 2013 | DOI: 10.1002/anie.201208471

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      Enantio- and regioselective: The intramolecular enantioselective aminofluorination of unactivated olefins was achieved by using a chiral iodo(III) difluoride salt. A highly regioselective aminofluorination of styrenes to access 2-fluoro-2-phenylethanamines was also developed.

    11. Heterogeneous Catalysis

      Enhancing Electrocatalytic Oxygen Reduction on MnO2 with Vacancies (pages 2474–2477)

      Prof. Dr. Fangyi Cheng, Tianran Zhang, Yi Zhang, Jing Du, Xiaopeng Han and Prof. Dr. Jun Chen

      Article first published online: 25 JAN 2013 | DOI: 10.1002/anie.201208582

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      Oxygen-vacant nanocrystalline MnO2 has been prepared by the simple process of annealing pristine oxide in Ar or O2. Both experimental and computational studies indicate that the catalytic activity of MnO2 towards oxygen reduction is enhanced by introducing a modest concentration of oxygen vacancies.

    12. Sonoluminescence

      The Origin of Isotope Effects in Sonoluminescence Spectra of Heavy and Light Water (pages 2478–2481)

      Dr. Abdoul Aziz Ndiaye, Dr. Rachel Pflieger, Dr. Bertrand Siboulet and Dr. Sergey I. Nikitenko

      Article first published online: 25 JAN 2013 | DOI: 10.1002/anie.201208891

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      Bubble and peak: The isotope effects in the sonoluminescence spectra of light and heavy water under ultrasound indicate the formation of a non-equilibrium plasma inside the collapsing cavitation bubbles. The picture demonstrates the active cavitation zones in water at 204 kHz.

    13. Electron Transfer

      Electrochemical Resolution of Multiple Redox Events for Graphene Quantum Dots (pages 2482–2485)

      Dhanraj B. Shinde and Prof. Vijayamohanan K. Pillai

      Article first published online: 29 JAN 2013 | DOI: 10.1002/anie.201208904

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      Quantum dots: A sequential, single-electron charging process of monodisperse graphene quantum dots (GQDs) encapsulated in a dodecylamine envelope, facilitating a capacitance of a few attofarads is reported. The average GQDs dimensions, as ascertained from high-resolution transmission electron microscopy and atomic force microscopy, of about 3±0.3, 2.6±0.2, and 2.2±0.3 nm control this unprecedented behavior (see picture).

    14. Heterocycles

      Catalytic Asymmetric Synthesis of Mixed 3,3′-Bisindoles and Their Evaluation as Wnt Signaling Inhibitors (pages 2486–2490)

      Prof. Dr. Takayoshi Arai, Yushi Yamamoto, Atsuko Awata, Kentaro Kamiya, Prof. Dr. Masami Ishibashi and Prof. Dr. Midori A. Arai

      Article first published online: 25 JAN 2013 | DOI: 10.1002/anie.201208918

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      TOP class: The first efficient catalytic asymmetric coupling reaction of indoles with isatin-derived nitroalkenes was accomplished by using a complex consisting of a chiral imidazoline aminophenol ligand (1; see scheme) and Cu(OTf)2. Biological activity of the newly formed chiral 3,3′-bisindoles was also confirmed in a Wnt signaling inhibitory assay.

    15. Spiro Compounds

      Interplay of Cascade Oxidative Cyclization and Hydride Shifts in the Synthesis of the ABC Spiroketal Ring System of Pectenotoxin-4 (pages 2491–2494)

      Prof. Timothy J. Donohoe and Radosław M. Lipiński

      Article first published online: 30 JAN 2013 | DOI: 10.1002/anie.201208919

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      Concepts: The formation of stereochemically defined bis-THF units through a double cyclization and a hydride-shift-initiated route to spiroketals is described (see scheme; Xc=chiral auxiliary). The resulting sequence has been used in a synthesis of the C1–16 fragment of the naturally occurring antitumor agent pectenotoxin-4.

    16. Spin–Spin Coupling

      You have full text access to this OnlineOpen article
      Weak Te,Te Interactions through the Looking Glass of NMR Spin–Spin Coupling (pages 2495–2498)

      Prof. Michael Bühl, Dr. Fergus R. Knight, Anezka Křístková, Dr. Irina Malkin Ondík, Dr. Olga L. Malkina, Rebecca A. M. Randall, Prof. Alexandra M. Z. Slawin and Prof. J. Derek Woollins

      Article first published online: 23 JAN 2013 | DOI: 10.1002/anie.201205998

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      Across the bay: J(125Te,125Te) spin–spin coupling is a highly sensitive probe into the electronic and geometric structure of 1,8-peri-substituted naphthalene tellurium derivatives. The coupling is related to the onset of multicenter bonding in these systems.

    17. Redox Chemistry

      Syntheses and Structural Studies of Tris(N-phenothiazinyl)borane and Its Radical Cation (pages 2499–2502)

      Dr. Shuichi Suzuki, Kohei Yoshida, Dr. Masatoshi Kozaki and Prof. Dr. Keiji Okada

      Article first published online: 21 JAN 2013 | DOI: 10.1002/anie.201208392

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      A radical comparison: The neutral (1) and radical cation (1.+) forms of tris(N-phenothiazinyl)borane were prepared and their molecular structures and spectral properties investigated. The results established that 1.+ possessed a localized radical cation on one of the phenothiazine (PTZ) rings. The crystal structure of 1.+ showed elongation of the B[BOND]N bond bound to the PTZ.+ ring (B[BOND]N1: 1.53 Å).

    18. Natural Products

      Stereoselective Total Synthesis of (+)-Giganin and Its C10 Epimer by Using Late-Stage Lithiation–Borylation Methodology (pages 2503–2506)

      Catherine J. Fletcher, Dr. Katherine M. P. Wheelhouse and Prof. Varinder K. Aggarwal

      Article first published online: 25 JAN 2013 | DOI: 10.1002/anie.201208403

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      The first total synthesis of (+)-giganin and its unnatural diastereoisomer (+)-C10-epi-giganin has been completed in a total of 13 linear steps, and 7 % and 8 % overall yield, respectively (see scheme; (-)-sp= (-)-sparteine, (+)-sps=(+)-sparteine surrogate). Lithiation–borylation methodology has been successfully applied in the key step, to couple together advanced intermediates with very high diastereoselectivity, thus demonstrating its power as a tool for total synthesis.

    19. Organosilicon Chemistry

      An Organosilicon Cluster with an Octasilacuneane Core: A Missing Silicon Cage Motif (pages 2507–2510)

      Dr. Shintaro Ishida, Dr. Kyohei Otsuka, Yuki Toma and Prof. Dr. Soichiro Kyushin

      Article first published online: 30 JAN 2013 | DOI: 10.1002/anie.201208506

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      Cagey silicon: A silicon cluster, consisting of sixteen silicon atoms and composed of an octasilacuneane core (red, see picture) fused with cyclotetrasilanes (orange), was synthesized by reductive tetramerization of tetrachlorocyclotetrasilane. Analytical and theoretical studies reveal the unique structural and electronic features of this organosilicon cluster.

    20. Solvent-Free Nanofluids

      Organosiloxane Supramolecular Liquids—Surface-Energy-Driven Phase Transitions (pages 2511–2515)

      Prof. Dr. John Texter, Dr. Kejian Bian, Dan Chojnowski and Joe Byrom

      Article first published online: 22 JAN 2013 | DOI: 10.1002/anie.201208725

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      Autocondensation of organoalkoxysilanes and subsequent anion exchange produces organosiloxane supramolecular liquids which are core-free and solvent-free nanoparticle nanofluids. This hybrid supramolecular liquid, [C81H156NO3S(SiO[2>x>3/2])]y, exhibits (see TEM image; 200 nm width) interparticle menisci and softness (from imputed deformations) of interparticle potential.

    21. Reaction Mechanisms

      Catalytic Reduction of CO2 to CO by Using Zinc(II) and In Situ Generated Carbodiphosphoranes (pages 2516–2519)

      Dr. Roman Dobrovetsky and Prof. Dr. Douglas W. Stephan

      Article first published online: 31 JAN 2013 | DOI: 10.1002/anie.201208817

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      Playing it ‘CO'ol: CO2 is catalytically reduced to CO with concurrent oxidation of phosphine to phosphineoxide by using an in situ generated catalyst derived from a carbodiphosphorane and zinc(II).

    22. Nanostructures

      Palladium-Based Nanostructures with Highly Porous Features and Perpendicular Pore Channels as Enhanced Organic Catalysts (pages 2520–2524)

      Dr. Xiaoqing Huang, Dr. Yongjia Li, Dr. Yu Chen, Dr. Enbo Zhou, Dr. Yuxi Xu, Hailong Zhou, Prof. Xiangfeng Duan and Prof. Yu Huang

      Article first published online: 30 JAN 2013 | DOI: 10.1002/anie.201208901

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      Channeling a good catalyst: Highly porous palladium nanostructures (pPdNs) with perpendicular pore channels (see picture) were prepared under mild conditions. The combination of high surface area and rich edge/corner atoms gives pPdNs better catalytic performance than known Pd catalysts for the hydrogenation of nitrobenzene and styrene and the Suzuki coupling reaction.

    23. Enantioselective Catalysis

      Catalytic Asymmetric C[BOND]N Bond Formation: Phosphine-Catalyzed Intra- and Intermolecular γ-Addition of Nitrogen Nucleophiles to Allenoates and Alkynoates (pages 2525–2528)

      Dr. Rylan J. Lundgren, Dr. Ashraf Wilsily, Dr. Nicolas Marion, Dr. Cong Ma, Dr. Ying Kit Chung and Prof. Gregory C. Fu

      Article first published online: 21 JAN 2013 | DOI: 10.1002/anie.201208957

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      Pin the amine on the gamma: A new method has been developed for the γ-addition of nitrogen nucleophiles to γ-substituted alkynoates or allenoates through intra- and intermolecular processes that are catalyzed by spirophosphine 1 (see scheme). An asymmetric version of this reaction affords enantioenriched pyrrolidines, indolines, and γ-amino-α,β-unsaturated carbonyl compounds.

    24. Synthetic Methods

      Copper-Catalyzed Intermolecular Aminocyanation and Diamination of Alkenes (pages 2529–2533)

      Hongwei Zhang, Weiya Pu, Dr. Tao Xiong, Dr. Yan Li, Xue Zhou, Kai Sun, Prof. Dr. Qun Liu and Prof. Dr. Qian Zhang

      Article first published online: 25 JAN 2013 | DOI: 10.1002/anie.201209142

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      ′N′ front and center: The facile construction of C[BOND]N bonds by the generation of nitrogen-centred radicals from N-fluorobenzenesulfonimide results in the aminative difuctionalization of alkenes. The first copper-catalyzed intermolecular aminocyanation of alkenes and diamination of styrenes were realized. Si–F and B–F interactions play a significant role in the reaction.

    25. Enzyme Catalysis

      Multistep Enzymatic Synthesis of Long-Chain α,ω-Dicarboxylic and ω-Hydroxycarboxylic Acids from Renewable Fatty Acids and Plant Oils (pages 2534–2537)

      M. Sc. Ji-Won Song, M. Sc. Eun-Yeong Jeon, M. Sc. Da-Hyun Song, M. Sc. Hyun-Young Jang, Prof. Uwe T. Bornscheuer, Prof. Deok-Kun Oh and Prof. Jin-Byung Park

      Article first published online: 30 JAN 2013 | DOI: 10.1002/anie.201209187

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      A multistep enzyme catalysis was successfully implemented to produce long-chain α,ω-dicarboxylic and ω-hydroxycarboxylic acids from renewable fatty acids and plant oils. Sebacic acid as well as ω-hydroxynonanoic acid and ω-hydroxytridec-11-enoic acid were produced from oleic and ricinoleic acid.

    26. Catalytic Hydrogenation

      Replacing Phosphorus with Sulfur for the Efficient Hydrogenation of Esters (pages 2538–2542)

      Dr. Denis Spasyuk, Samantha Smith and Prof. Dmitry G. Gusev

      Article first published online: 28 JAN 2013 | DOI: 10.1002/anie.201209218

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      Catalyst tune-up: A readily available, air-stable amino–sulfide catalyst, [RuCl2(PPh3){HN(C2H4SEt)2}], has been developed. This complex displays outstanding efficiency for the hydrogenation of a broad range of substrates with C[DOUBLE BOND]X bonds (esters, ketones, imines), as well as for the acceptorless dehydrogenative coupling of ethanol to ethyl acetate (see scheme).

    27. Synthetic Methods

      Catalyst-Free Intramolecular Formal Carbon Insertion into σ-C[BOND]C Bonds: A New Approach toward Phenanthrols and Naphthols (pages 2543–2546)

      Ying Xia, Peiyuan Qu, Zhenxing Liu, Rui Ge, Qing Xiao, Dr. Yan Zhang and Prof. Dr. Jianbo Wang

      Article first published online: 29 JAN 2013 | DOI: 10.1002/anie.201209269

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      The different reactivity of two kinds of carbonyl groups in keto aldehyde substrates has been exploited for the synthesis of phenanthrols, naphthols, and their heteroatom-containing analogues. Key to this highly efficient and robust methodology is the catalyst-free intramolecular formal diazo carbon insertion of N-tosylhydrazones into keto C[BOND]C bonds (see scheme).

    28. C-H Alkylation

      Copper-Catalyzed Direct Secondary and Tertiary C[BOND]H Alkylation of Azoles through a Heteroarene–Amine–Aldehyde/Ketone Coupling Reaction (pages 2547–2550)

      Dipak D. Vachhani, Dr. Abhishek Sharma and Prof. Dr. Erik Van der Eycken

      Article first published online: 22 JAN 2013 | DOI: 10.1002/anie.201209312

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      Coupling the strangers: A copper-catalyzed three-component heteroarene–amine–aldehyde/ketone coupling affords a novel approach to the hitherto difficult direct secondary/tertiary C[BOND]H alkylation of azoles. This simple method allows the facile installation of diversely substituted, branched and nitrogen-containing alkyl or alkaloid side chains on the azole moiety by using readily available starting materials (see scheme).

    29. Heterocycles

      Diastereoselective Intramolecular Allyl Transfer from Allyl Carbamate Accompanied by 5-endo-trig Ring Closure (pages 2551–2554)

      Oskari K. Karjalainen, Dr. Martin Nieger and Ari M. P. Koskinen

      Article first published online: 22 JAN 2013 | DOI: 10.1002/anie.201209443

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      To All(oc) involved: A palladium-catalyzed formal 5-endo-trig heteroannulation of enones generated in situ from amino acid derived β-keto nitriles has been realized (see scheme; Alloc=allyl carbamate). The reaction proceeds with allyl-group transfer from the carbamate protecting group to generate two new contiguous stereocenters, including one quaternary center, with high selectivity.

    30. Synthetic Methods

      Enantioselective Copper-Catalyzed Intramolecular Phenolic O[BOND]H Bond Insertion: Synthesis of Chiral 2-Carboxy Dihydrobenzofurans, Dihydrobenzopyrans, and Tetrahydrobenzooxepines (pages 2555–2558)

      Xiao-Guang Song, Prof. Shou-Fei Zhu, Xiu-Lan Xie and Prof. Qi-Lin Zhou

      Article first published online: 31 JAN 2013 | DOI: 10.1002/anie.201209455

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      Efficient: A copper-catalyzed enantioselective intramolecular insertion of carbenoids into phenolic O[BOND]H bonds has been developed. This method can be used for the synthesis of the title compounds in high yields and excellent enantioselectivities under mild and neutral conditions (see scheme). NaBArF=sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate.

    31. Heterocycles

      Copper-Catalyzed Aerobic Intramolecular Dehydrogenative Cyclization of N,N-Disubstituted Hydrazones through Cmath image[BOND]H Functionalization (pages 2559–2563)

      Dr. Guangwu Zhang, Yan Zhao and Prof. Dr. Haibo Ge

      Article first published online: 23 JAN 2013 | DOI: 10.1002/anie.201209618

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      An aerobic activity: The title reaction proceeds through an oxidation/cyclization/aromatization sequence under an atmosphere of O2 (see scheme; DBU=1,8-diazabicyclo[5.4.0]undec-7-ene, DCE=1,2-dichloroethane, DMS=dimethylsulfide). This coupling reaction is the first to proceed via an iminium intermediate for a Cmath image[BOND]H bond-functionalization process, and provides an environmentally friendly and atom-efficient access to substituted pyrazoles.

    32. Conjugated Polymers

      Large-Scale Hierarchically Structured Conjugated Polymer Assemblies with Enhanced Electrical Conductivity (pages 2564–2568)

      Dr. Wei Han, Dr. Ming He, Dr. Myunghwan Byun, Bo Li and Prof. Zhiqun Lin

      Article first published online: 25 JAN 2013 | DOI: 10.1002/anie.201209632

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      Stripes on a plane: A set of highly ordered microscopic stripes (purple; see scheme) were produced over a large area by using controlled evaporative self-assembly in a cylinder-on-Si geometry of conjugated homopolymers or all-conjugated diblock copolymer (P3BHT). The crystallinity of the as-prepared assemblies of P3BHT was greatly improved following chloroform vapor annealing, resulting in a fourfold increase in electrical conductivity.

    33. Enzyme Mechanism

      Use of a Metallopeptide-Based Mimic Provides Evidence for a Proton-Coupled Electron-Transfer Mechanism for Superoxide Reduction by Nickel-Containing Superoxide Dismutase (pages 2569–2572)

      Prof. Jason Shearer

      Article first published online: 22 JAN 2013 | DOI: 10.1002/anie.201209746

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      Sneaky little SOD! A metallopeptide-based mimic of nickel-containing superoxide dismutase was used to probe the mechanism of superoxide reduction by the metalloenzyme. Kinetic studies suggest a proton-coupled electron-transfer mechanism; large H/D kinetic isotope effects (KIE) are observed. XAS studies suggest the transferred H-atom is in the form of a NiII-S(H)-Cys moiety (see graph).

    34. Asymmetric Catalysis

      Catalytic Asymmetric Three-Component Synthesis of Homoallylic Amines (pages 2573–2576)

      Dr. Shikha Gandhi and Prof. Dr. Benjamin List

      Article first published online: 25 JAN 2013 | DOI: 10.1002/anie.201209776

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      It takes three to make things go right: The first direct asymmetric three-component reaction of aldehydes, carbamates, and allyltrimethylsilane leading to enantioenriched homoallylic amines has been developed using a new chiral disulfonimide catalyst (see scheme). The method employs readily available, inexpensive, and nontoxic starting materials and is applicable to both aromatic and aliphatic aldehydes.

    35. C[BOND]H Activation

      Rhodium(III)-Catalyzed C[BOND]C Coupling between Arenes and Aziridines by C[BOND]H Activation (pages 2577–2580)

      Prof. Dr. Xingwei Li, Songjie Yu, Fen Wang, Prof.Dr. Boshun Wan and Xinzhang Yu

      Article first published online: 31 JAN 2013 | DOI: 10.1002/anie.201209887

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      Making C[BOND]C from C[BOND]H: [{RhCp*Cl2}2]/AgSbF6 (Cp*=pentamethylcyclopentadienyl) can regioselectively catalyze the C[BOND]C coupling of arenes with aziridines by a C[BOND]H activation pathway. An eight-membered rhodacyclic intermediate resulting from the insertion of the Rh[BOND]C bond into the aziridine was isolated.

    36. Graphene

      You have full text access to this OnlineOpen article
      The Multiradical Character of One- and Two-Dimensional Graphene Nanoribbons (pages 2581–2584)

      Dr. Felix Plasser, Dr. Hasan Pašalić, Prof. Martin H. Gerzabek, Dr. Florian Libisch, Rafael Reiter, Prof. Joachim Burgdörfer, Dr. Thomas Müller, Dr. Ron Shepard and Prof. Hans Lischka

      Article first published online: 28 JAN 2013 | DOI: 10.1002/anie.201207671

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      When is an acene stable? The pronounced multiradical character of graphene nanoribbons of different size and shape was investigated with high-level multireference methods. Quantitative information based on the number of effectively unpaired electrons leads to specific estimates of the chemical stability of graphene nanostructures.

    37. Organocatalysis

      NHC-Catalyzed Hydroacylation of Styrenes (pages 2585–2589)

      Michael Schedler, Dr. Duo-Sheng Wang and Prof. Dr. Frank Glorius

      Article first published online: 25 JAN 2013 | DOI: 10.1002/anie.201209291

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      New hydroacylation catalysts: Highly electron-rich N-heterocyclic carbenes (NHCs) facilitate the intermolecular hydroacylation of unstrained olefins. This unprecedented organocatalytic coupling joins simple and abundant aldehydes and styrenes to yield valuable ketone products. EWG=electron-withdrawing group, EDG=electron-donating group.

    38. Polysulfate Ligands

      Bis(tetrasulfato)palladate, [Pd(S4O13)2]2− (pages 2590–2592)

      Jörn Bruns, Prof. Dr. Thorsten Klüner and Prof. Dr. Mathias S. Wickleder

      Article first published online: 29 JAN 2013 | DOI: 10.1002/anie.201209346

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      SOS: The first coordination compound containing polysulfate ligands was obtained under harsh conditions from the reaction of K2[PdCl4] and SO3. The compound contains a Pd2+ ion coordinated by two chelating tetrasulfate anions (see structure, Pd red, S yellow, O blue), which leads to a significant stabilization of the polysulfate anions compared to their uncoordinated analogues.

    39. Dual Gold Catalysis

      Mechanistic Switch in Dual Gold Catalysis of Diynes: C(sp3)–H Activation through Bifurcation—Vinylidene versus Carbene Pathways (pages 2593–2598)

      M. Sc. Max M. Hansmann, Dr. Matthias Rudolph, Dr. Frank Rominger and Prof. Dr.  A. Stephen K. Hashmi

      Article first published online: 30 JAN 2013 | DOI: 10.1002/anie.201208777

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      The other side of the mountain: Changing the framework of diyne systems opens up new cyclization modes for dual gold catalysis. Instead of a 5-endo cyclization and gold vinylidenes a 6-endo cyclization gives rise to gold-stabilized carbenes as key intermediates for selective C[BOND]H insertions.

    40. Boron Mimetics

      BN/CC Isosteric Compounds as Enzyme Inhibitors: N- and B-Ethyl-1,2-azaborine Inhibit Ethylbenzene Hydroxylation as Nonconvertible Substrate Analogues (pages 2599–2601)

      Daniel H. Knack, Jonathan L. Marshall, Gregory P. Harlow, Agnieszka Dudzik, Dr. Maciej Szaleniec, Prof. Dr. Shih-Yuan Liu and Prof. Dr. Johann Heider

      Article first published online: 28 JAN 2013 | DOI: 10.1002/anie.201208351

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      Good substrate gone bad! BN/CC isosterism of ethylbenzene leads to N-ethyl-1,2-azaborine and B-ethyl-1,2-azaborine. In contrast to ethylbenzene, which is the substrate for ethylbenzene dehydrogenase (EbDH), N-ethyl-1,2-azaborine (see scheme; Fc=Ferricenium tetrafluoroborate) and B-ethyl-1,2-azaborine are strong inhibitors of EbDH. Thus, the changes provided by BN/CC isosterism can lead to new biochemical reactivity.

    41. Two-Dimensional IR Spectroscopy

      A Hydrogen-Bond Flip-Flop through a Bjerrum-Type Defect (pages 2602–2605)

      Martin Olschewski, Dr. Jörg Lindner and Prof. Dr. Peter Vöhringer

      Article first published online: 18 FEB 2013 | DOI: 10.1002/anie.201208625

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      Back and forth: Femtosecond two-dimensional infrared exchange spectroscopy was used to study the dynamics of the reversal of an intramolecular hydrogen bond. The H-bond reversal resembles a flip-flop motion that is facilitated by two concerted disrotatory torsional isomerizations and that occurs on a time scale of about 2 ps.

    42. Vitamin B12 Antimetabolites

      Access to Organometallic Arylcobaltcorrins through Radical Synthesis: 4-Ethylphenylcobalamin, a Potential “Antivitamin B12 (pages 2606–2610)

      Mag. Markus Ruetz, Dr. Carmen Gherasim, Prof. Dr. Karl Gruber, Dr. Sergey Fedosov, Prof. Dr. Ruma Banerjee and Prof. Dr. Bernhard Kräutler

      Article first published online: 13 FEB 2013 | DOI: 10.1002/anie.201209651

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      Locked B12: 4-Ethylphenylcobalamin, a novel organometallic arylcobalamin, has been synthesized in a radical reaction. This vitamin B12 antimetabolite features a strong Co[BOND]C bond, and represents a “locked” form of vitamin B12 (see picture). It may be used in animal studies to induce functional vitamin B12 deficiency artificially to help clarify still controversial issues related to the pathophysiology of vitamin B12 deficiency.

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