Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 14

April 2, 2013

Volume 52, Issue 14

Pages 3777–4038

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. You have free access to this content
      Cover Picture: Glaser Coupling at Metal Surfaces (Angew. Chem. Int. Ed. 14/2013) (page 3777)

      Dr. Hong-Ying Gao, Dr. Hendrik Wagner, Dr. Dingyong Zhong, Dr. Jörn-Holger Franke, Prof. Dr. Armido Studer and Prof. Dr. Harald Fuchs

      Version of Record online: 13 MAR 2013 | DOI: 10.1002/anie.201301670

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      On-surface synthesis enables the construction of defined nanostructures directly at surfaces through the covalent coupling of suitable organic precursors. These processes are carried out under ultrahigh-vacuum conditions and are monitored by scanning tunneling microscopy. In their Communication on page 4024 ff., A. Studer, H. Fuchs, and co-workers present a systematic study of the homocoupling of alkynes (Glaser coupling) as a versatile strategy for the construction of conjugated polymers at various metal surfaces.

    2. You have free access to this content
      Inside Cover: Incorporation of Vinyl Chloride in Insertion Polymerization (Angew. Chem. Int. Ed. 14/2013) (page 3778)

      Hannes Leicht, Dr. Inigo Göttker-Schnetmann and Prof. Dr. Stefan Mecking

      Version of Record online: 20 MAR 2013 | DOI: 10.1002/anie.201301461

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      Insertion polymerization allows microstructure control in the synthesis of polymers made from vinyl chloride, the practical use of which is limited by their thermal stability, owing to microstructure defects from free-radical polymerization. In their Communication on page 3963 ff., S. Mecking and co-workers report that catalytic insertion copolymerization of ethylene and vinyl chloride is feasible and gives chlorinated polymers. Cover art: I. Göttker-Schnetmann, H. Leicht, and S. Mecking, based on a photograph by J. Holthof.

    3. You have free access to this content
      Inside Back Cover: Carbon Nanotubes Bridged with Graphene Nanoribbons and Their Use in High-Efficiency Dye-Sensitized Solar Cells (Angew. Chem. Int. Ed. 14/2013) (page 4039)

      Zhibin Yang, Mingkai Liu, Chao Zhang, Weng Weei Tjiu, Prof. Tianxi Liu and Prof. Huisheng Peng

      Version of Record online: 21 FEB 2013 | DOI: 10.1002/anie.201301080

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      Multiwalled carbon nanotubes can be partially unzipped to produce nanoribbons that bridge the nanotubes. As shown by T. Liu, H. Peng, and co-workers in their Communication on page 3996 ff., this unique structure favors rapid charge transport when used as a counter electrode in dye-sensitized solar cells, resulting in a maximum energy conversion efficiency of 8.23 %.

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      Back Cover: Supramolecular Control of Selectivity in Hydroformylation of Vinyl Arenes: Easy Access to Valuable β-Aldehyde Intermediates (Angew. Chem. Int. Ed. 14/2013) (page 4040)

      Paweł Dydio and Prof. Dr. Joost N. H. Reek

      Version of Record online: 4 MAR 2013 | DOI: 10.1002/anie.201301447

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      Precise selectivity control in transition-metal catalysis is critical for modern chemical synthesis. In their Communication on page 3878 ff., J. N. H. Reek and P. Dydio demonstrate that substrate preorganization through noncovalent supramolecular interactions with the ligand is a powerful enabling strategy to control selectivity, and gives access to usually unfavored products. As exemplified for the Rh-catalyzed hydroformylation of vinyl arenes, this approach opens up new avenues in the synthesis of valuable compounds.

  2. Editorial

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
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      Editorial: Effective Presentations—A Must (pages 3780–3781)

      Prof. Dr. Craig J. Hawker

      Version of Record online: 14 MAR 2013 | DOI: 10.1002/anie.201209795

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  3. Graphical Abstract

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

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. You have free access to this content
      Corrigendum: Electron-Induced Spin Crossover of Single Molecules in a Bilayer on Gold (page 3796)

      Dr. Thiruvancheril G. Gopakumar, Dr. Francesca Matino, Holger Naggert, Dr. Alexander Bannwarth, Prof. Dr. Felix Tuczek and Prof. Dr. Richard Berndt

      Version of Record online: 26 MAR 2013 | DOI: 10.1002/anie.201301569

      This article corrects:

      Electron-Induced Spin Crossover of Single Molecules in a Bilayer on Gold1

      Vol. 51, Issue 25, 6262–6266, Version of Record online: 8 MAY 2012

  5. News

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

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. Sukbok Chang (page 3804)

      Version of Record online: 11 DEC 2012 | DOI: 10.1002/anie.201208010

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      “My favorite saying is “be persistent and never give up”. I admire anyone who inspires others and creates new ways of thinking. …” This and more about Sukbok Chang can be found on page 3804.

  7. Book Review

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. Lehrbuch der Physikalischen Chemie. 6th Edition, with Workbook (in German). By Gerd Wedler and Hans-Joachim Freund. (page 3805)

      Martin K. Beyer

      Version of Record online: 8 MAR 2013 | DOI: 10.1002/anie.201300430

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      Wiley-VCH, Weinheim, 2012. 1146 pp., hardcover, € 89.90.—ISBN 978-3527329090

  8. Highlight

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

      Squeezing New Life Out of Polymers (pages 3806–3808)

      Johnathan N. Brantley, Kelly M. Wiggins and Prof. Christopher W. Bielawski

      Version of Record online: 25 FEB 2013 | DOI: 10.1002/anie.201210025

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      Pressed for results: Mechanical forces can be used to generate reactive small molecules, such as mineral acids and hydrogen peroxide, from appropriately designed polymeric materials. These novel mechanically responsive scaffolds set the foundation for using mechanochemistry to access new classes of self-healing materials and to drive small-scale synthetic reactions.

  9. Minireview

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

      Large N-Heteroacenes: New Tricks for Very Old Dogs? (pages 3810–3821)

      Prof. Uwe H. F. Bunz, Dipl.-Chem. Jens U. Engelhart, Dipl.-Chem. Benjamin D. Lindner and M. Sc. Manuel Schaffroth

      Version of Record online: 18 FEB 2013 | DOI: 10.1002/anie.201209479

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      Electron-transporting alternatives to pentacene? Since 2010, several research groups have succeeded in synthesizing substituted diaza- and tetraazapentacenes as well as structurally similar tetraaza- and hexaazahexacenes. The symmetrical tetraazapentacene (see structure; C gray, H white, N blue, Si tan) has been investigated as an electron-transporting material in thin-film transistors.

  10. Review

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. Diels–Alder Reaction

      Industrial Applications of the Diels–Alder Reaction (pages 3822–3863)

      Dr. Jacques-Alexis Funel and Dr. Stefan Abele

      Version of Record online: 27 FEB 2013 | DOI: 10.1002/anie.201201636

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      Diels–Alder reactions on a kg scale: The Diels–Alder reaction counts as one of the most popular transformations for the efficient synthesis of complex molecules, but its application in the industrial synthesis of pharmacologically active ingredients and agrochemicals as well as flavors and fragrances is less known. This Review gives examples of large-scale applications (>1 kg) from a process research and development perspective.

  11. Communications

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

      Telluronium Ions as σ-Acceptor Ligands (pages 3864–3868)

      Tzu-Pin Lin and Prof. Dr. François P. Gabbaï

      Version of Record online: 18 FEB 2013 | DOI: 10.1002/anie.201300337

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      A duel between lone pairs: A telluronium cation has been successfully installed in the coordination sphere of a palladium(II) complex. Despite the presence of a lone pair centered on the Group 16 element, the telluronium ion acts as a Z-ligand and accepts a d-electron pair from the palladium atom.

    2. Organocatalysis

      Hydrogen-Bond-Directed Enantioselective Decarboxylative Mannich Reaction of β-Ketoacids with Ketimines: Application to the Synthesis of Anti-HIV Drug DPC 083 (pages 3869–3873)

      Hai-Na Yuan, Shuai Wang, Jing Nie, Wei Meng, Dr. Qingwei Yao and Prof. Jun-An Ma

      Version of Record online: 4 MAR 2013 | DOI: 10.1002/anie.201210361

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      Key to success: The title reaction provides facile access to enantioenriched 3,4-dihydroquinazolin-2(1H)-ones containing a quaternary stereogenic center in high yields with excellent enantioselectivities. Subsequent transformations lead to the convenient preparation of the anti-HIV drug DPC 083 and N-fused polycyclic compounds without loss of enantiomeric excess.

    3. Molecular Probes

      Red Fluorescent Probe for Monitoring the Dynamics of Cytoplasmic Calcium Ions (pages 3874–3877)

      Takahiro Egawa, Kazuhisa Hirabayashi, Dr. Yuichiro Koide, Chiaki Kobayashi, Dr. Naoya Takahashi, Dr. Tomoko Mineno, Dr. Takuya Terai, Dr. Tasuku Ueno, Dr. Toru Komatsu, Dr. Yuji Ikegaya, Prof. Norio Matsuki, Prof. Tetsuo Nagano and Dr. Kenjiro Hanaoka

      Version of Record online: 25 FEB 2013 | DOI: 10.1002/anie.201210279

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      We see red (and yellow and green): Probe 1 was developed for the visualization of cytoplasmic Ca2+, a pivotal second messenger in many biological responses. The new probe is suitable for multicolor imaging for the simultaneous detection of metal ions or proteins and is superior to the existing red fluorescent probe Rhod-2 for the monitoring of cytoplasmic Ca2+ oscillation in cultured cells (see fluorescence images of cells with 1 (top) and Rhod-2 (bottom)).

    4. Homogeneous Catalysis

      Supramolecular Control of Selectivity in Hydroformylation of Vinyl Arenes: Easy Access to Valuable β-Aldehyde Intermediates (pages 3878–3882)

      Paweł Dydio and Prof. Dr. Joost N. H. Reek

      Version of Record online: 18 FEB 2013 | DOI: 10.1002/anie.201209582

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      Go against the flow! A rationally designed regioselective hydroformylation catalyst, [Rh/L], in which noncovalent ligand–substrate interactions allow the unprecedented reversal of selectivity from the typical α-aldehyde to the otherwise unfavored product β-aldehyde, is reported. This catalytic system opens up novel and sustainable synthetic pathways to important intermediates for the fine-chemicals industry.

    5. Multifunctional Reactions

      One-Pot Procedure for the Introduction of Three Different Bonds onto Terminal Alkynes through N-Sulfonyl-1,2,3-Triazole Intermediates (pages 3883–3886)

      Dr. Tomoya Miura, Takamasa Tanaka, Tsuneaki Biyajima, Dr. Akira Yada and Prof. Dr. Masahiro Murakami

      Version of Record online: 25 FEB 2013 | DOI: 10.1002/anie.201209603

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      Triple strike: Copper(I) and rhodium(II) complexes can cooperate to facilely convert terminal alkynes into α-allyl-α-amino ketones through triazole intermediates. This synthetic process achieves the regioselective multifunctionalization of terminal alkynes with the formation of C[BOND]C, C[BOND]O, and C[BOND]N bonds in one pot.

    6. Lithium–Oxygen Batteries

      Synthesis of Perovskite-Based Porous La0.75Sr0.25MnO3 Nanotubes as a Highly Efficient Electrocatalyst for Rechargeable Lithium–Oxygen Batteries (pages 3887–3890)

      Dr. Ji-Jing Xu, Dan Xu, Zhong-Li Wang, Heng-Guo Wang, Lei-Lei Zhang and Prof. Dr. Xin-Bo Zhang

      Version of Record online: 27 FEB 2013 | DOI: 10.1002/anie.201210057

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      Tailoring an electrocatalyst: The synergistic effect of the high catalytic activity and the unique hollow channel structure of the perovskite-based porous La0.75Sr0.25MnO3 nanotube electrocatalyst endows the Li-O2 battery with a high specific capacity, superior rate capability, and good cycle stability (see picture).

    7. High-Pressure Chemistry

      Pressure-Induced Water Insertion in Synthetic Clays (pages 3891–3895)

      Dr. Shujie You, Daniel Kunz, Matthias Stöter, Hussein Kalo, Bernd Putz, Prof. Josef Breu and Dr. Alexandr V. Talyzin

      Version of Record online: 27 FEB 2013 | DOI: 10.1002/anie.201210060

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      A high-pressure study of a synthetic smectite (Na-fluorohectorite) immersed in liquid media was performed using in situ synchrotron X-ray diffraction in a diamond anvil cell. A reversible phase transition because of the insertion of an additional water layer was observed for this material at 1.7 GPa. No similar transition was found when methanol was used as a pressure medium (see picture).

    8. Crystal Nitrosylation

      Preparation of the Elusive [(por)Fe(NO)(O-ligand)] Complex by Diffusion of Nitric Oxide into a Crystal of the Precursor (pages 3896–3900)

      Dr. Nan Xu, Lauren E. Goodrich, Dr. Nicolai Lehnert, Dr. Douglas R. Powell and Dr. George B. Richter-Addo

      Version of Record online: 4 MAR 2013 | DOI: 10.1002/anie.201208063

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      A crystal-gas method was used to prepare neutral [(por)Fe(NO)(O-ligand)] complexes. [(por)Fe(NO)(OC([DOUBLE BOND]O)CF3)] has an almost linear Fe[BOND]NO moiety. Porphyrin molecules move dramatically in the crystal upon NO diffusion into the lattice and binding to Fe. DFT calculations on this and related complexes provide insight into the trans effects of axial ligands on the Fe[BOND]NO angle.

    9. Drug Delivery

      Systemic Delivery of microRNA-34a for Cancer Stem Cell Therapy (pages 3901–3905)

      Sanjun Shi, Lu Han, Prof. Tao Gong, Prof. Zhirong Zhang and Prof. Xun Sun

      Version of Record online: 28 FEB 2013 | DOI: 10.1002/anie.201208077

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      Delivered: A solid lipid nanoparticle (SLN) system was developed to deliver microRNA-34a (miR-34a) relevant for cancer stem cell (CSC) therapy into lung tissues. In miR-34a-containing SLNs (miSLNs-34a), miR-34a is protected from degradation in the serum and its cellular-transfection efficiency in vitro is increased. Thus, treatment with miSLNs-34a results in a higher probability of survival of CSC-bearing mice (see picture).

    10. Molecular Switches

      Toward Functional Molecular Devices Based on Graphene–Molecule Junctions (pages 3906–3910)

      Yang Cao, Shaohua Dong, Song Liu, Prof. Zhongfan Liu and Prof. Xuefeng Guo

      Version of Record online: 4 MAR 2013 | DOI: 10.1002/anie.201208210

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      Building bridges: Molecular functionalities can be installed into electronic devices having graphene–molecule junctions generated by the dash-line lithographic (DLL) method. When a sulfonic acid modified azobenzene unit served as the bridge, the conductance could be switched reversibly by irradiation with light of different wavelengths and by exposure to solutions of different pH. Other molecular transport junctions were generated by metal-ion coordination.

    11. Membrane Proteins

      Internal Dynamics of the Homotrimeric HIV-1 Viral Coat Protein gp41 on Multiple Time Scales (pages 3911–3915)

      Dr. Nils-Alexander Lakomek, Joshua D. Kaufman, Dr. Stephen J. Stahl, Dr. John M. Louis, Dr. Alexander Grishaev, Dr. Paul T. Wingfield and Dr. Ad Bax

      Version of Record online: 28 FEB 2013 | DOI: 10.1002/anie.201207266

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      Always on the move: Solution NMR spectroscopy revealed a high degree of intrinsic mobility for the homotrimeric viral coat protein gp41: a prehairpin intermediate (left) may sample a range of relative orientations of the C-terminal and N-terminal heptad repeats, possibly in exchange with a low population of the late-fusion six-helical bundle (right; FP: fusion peptide, TM: transmembrane helix).

    12. Protein PEGylation

      Self-Liganded Suzuki–Miyaura Coupling for Site-Selective Protein PEGylation (pages 3916–3921)

      Dr. Anaëlle Dumas, Christopher D. Spicer, Dr. Zhanghua Gao, Dr. Tsuyoshi Takehana, Yuya A. Lin, Tohru Yasukohchi and Prof. Benjamin G. Davis

      Version of Record online: 25 FEB 2013 | DOI: 10.1002/anie.201208626

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      Building with PEGs: PEG–boronic acids, in the presence of simple Pd sources, are capable of acting as direct and effective Suzuki reagents in 70–98 % yield. When combined with non-natural amino acids, they allow efficient and direct, site-selective PEGylation of proteins at predetermined positions under biologically compatible conditions without the need for exogenous ligands.

    13. Artificial Metalloenzyme

      An Artificial Oxygenase Built from Scratch: Substrate Binding Site Identified Using a Docking Approach (pages 3922–3925)

      Charlène Esmieu, Dr. Mickaël V. Cherrier, Dr. Patricia Amara, Dr. Elodie Girgenti, Dr. Caroline Marchi-Delapierre, Dr. Frédéric Oddon, Marina Iannello, Adeline Jorge-Robin, Dr. Christine Cavazza and Dr. Stéphane Ménage

      Version of Record online: 25 FEB 2013 | DOI: 10.1002/anie.201209021

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      The substrate for an artificial iron monooxygenase was selected by using docking calculations. The high catalytic efficiency of the reported enzyme for sulfide oxidation was directly correlated to the predicted substrate binding mode in the protein cavity, thus illustrating the synergetic effect of the substrate binding site, protein scaffold, and catalytic site.

    14. Molecular Imaging

      A R2p/R1p Ratiometric Procedure to Assess Matrix Metalloproteinase-2 Activity by Magnetic Resonance Imaging (pages 3926–3930)

      Dr. Valeria Catanzaro, Dr. Concetta V. Gringeri, Dr. Valeria Menchise, Dr. Sergio Padovan, Dr. Cinzia Boffa, Dr. Walter Dastrù, Dr. Linda Chaabane, Dr. Giuseppe Digilio and Prof. Silvio Aime

      Version of Record online: 28 FEB 2013 | DOI: 10.1002/anie.201209286

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      Parametric MRI: A paramagnetic gadolinium-loaded liposome for the MRI assessment of the activity of matrix metalloproteinase-2 (MMP-2) is described. The assessment relies on a procedure that involves the ratio R2p/R1p between the transverse and longitudinal paramagnetic contributions to the water proton relaxation rate. This method is independent of the total gadolinium concentration.

    15. FLIM Biosensor

      Fluorescence Lifetime Imaging of Biosensor Peptide Phosphorylation in Single Live Cells (pages 3931–3934)

      Nur P. Damayanti, Prof. Laurie L. Parker and Prof. Joseph M. K. Irudayaraj

      Version of Record online: 28 FEB 2013 | DOI: 10.1002/anie.201209303

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      Better living through biochemistry: Phosphorylation of a Cy5-labeled Abl kinase peptide biosensor resulted in an extension of fluorescence lifetime in live cells. Time-correlated single photon counting fluorescence lifetime imaging (FLIM) enabled excellent signal-to-noise to visualize the subcellular patterns of this sensor (see picture). This strategy should be generalizable to other peptide-based kinase substrates for imaging of kinase activity in single cells.

    16. Peptide Conformational Analysis

      Crystal-Structure Analysis of cis-X-Pro-Containing Peptidomimetics: Understanding the Steric Interactions at cis X-Pro Amide Bonds (pages 3935–3939)

      Damodara N. Reddy, Gijo George and Dr. Erode N. Prabhakaran

      Version of Record online: 28 FEB 2013 | DOI: 10.1002/anie.201209517

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      Catch the twist: The cis Piv-Pro conformer (Piv=pivaloyl) of peptides is no longer inaccessible. Any cis X-Pro tertiary-amide-bond conformer can be stabilized in crystals of peptides by accommodating the unavoidable distortion of the dihedral angle of the peptide bond to the carbonyl group of the Pro residue (see picture), in this case through ni−1[RIGHTWARDS ARROW]πi* interactions. Steric clashes were not observed in the cis Piv-Pro rotamers studied.

    17. Photoresponsive Materials

      Photo- and Thermoresponsive Supramolecular Assemblies: Reversible Photorelease of K+ Ions and Constitutional Dynamics (pages 3940–3943)

      Ghislaine Vantomme and Prof. Jean-Marie Lehn

      Version of Record online: 28 FEB 2013 | DOI: 10.1002/anie.201210334

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      Freed at the flick of a photoswitch: An acyl hydrazone forms supramolecular assemblies upon the binding of specific salts, such as potassium thiocyanate. This process presents cation and anion selectivity as well as thermo- and photoreversibility (see scheme). In particular, the system displays photorelease of potassium cations and undergoes dynamic component exchange in the acyl hydrazone.

    18. Noncovalent Interactions

      Nanomechanics of Cation–π Interactions in Aqueous Solution (pages 3944–3948)

      Dr. Qingye Lu, Dongyeop X. Oh, Youngjin Lee, Prof. Yongseok Jho, Prof. Dong Soo Hwang and Prof. Hongbo Zeng

      Version of Record online: 28 FEB 2013 | DOI: 10.1002/anie.201210365

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      The first direct probing of the nanomechanics of cation–π interactions in aqueous media was accomplished by using a surface forces apparatus with complementary theoretical simulations. The tetraethylammonium (TEA) ion breaks the adhesion between poly-L-tryptophan (PTrp) and poly-L-lysine (PLL) with a 100 times higher sensitivity relative to the K+ ion (PS=polystyrene, PTyr=poly-L-tyrosine, and ACh=acetylcholine).

    19. Bioisosteres

      Direct Synthesis of Fluorinated Heteroarylether Bioisosteres (pages 3949–3952)

      Dr. Qianghui Zhou, Alessandro Ruffoni, Ryan Gianatassio, Dr. Yuta Fujiwara, Dr. Eran Sella, Prof. Dr. Doron Shabat and Prof. Dr. Phil S. Baran

      Version of Record online: 4 MAR 2013 | DOI: 10.1002/anie.201300763

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      (Bioiso)steering in a new direction: A modular synthesis of reagents (e.g. sodium difluoroethylsulfinate) that can be used for the direct incorporation of difluoroalkyl groups onto heterocycles is reported. The scope and generality of the incorporation of difluoroalkyl groups is exemplified with the difluoroethyl group and a proof of principle is shown for a general synthesis of fluorinated heteroarylether bioisosteres.

    20. Carbon Dots

      Highly Photoluminescent Carbon Dots for Multicolor Patterning, Sensors, and Bioimaging (pages 3953–3957)

      Shoujun Zhu, Qingnan Meng, Lei Wang, Prof. Junhu Zhang, Yubin Song, Han Jin, Prof. Kai Zhang, Prof. Hongchen Sun, Prof. Haiyu Wang and Prof. Bai Yang

      Version of Record online: 28 FEB 2013 | DOI: 10.1002/anie.201300519

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      Shine on you crazy dots: A rapid and high-output strategy allows the fabrication of polymer-like carbon dots (CDs) with quantum yields as high as ca. 80 %. This value is the highest reported to date for fluorescent carbon-based materials, and gives promise for their application in multicolor-patterning and biosensors.

    21. Protein–Protein Interactions

      A Genetically Encoded 19F NMR Probe for Tyrosine Phosphorylation (pages 3958–3962)

      Fahui Li, Pan Shi, Jiasong Li, Fan Yang, Tianyuan Wang, Wei Zhang, Feng Gao, Wei Ding, Dong Li, Juan Li, Ying Xiong, Jinpeng Sun, Weimin Gong, Changlin Tian and Jiangyun Wang

      Version of Record online: 28 FEB 2013 | DOI: 10.1002/anie.201300463

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      Simple and selective: Tyrosine phosphorylation is a pivotal post-translational modification which regulates the enzymatic activity, protein conformation, and protein–protein interactions. The highly efficient genetic incorporation of 3,5-difluorotyrosine (F2Y) in E. coli and the use of F2Y as a 19F NMR probe for the tyrosine phosphorylation are reported (see picture).

    22. Copolymerization

      Incorporation of Vinyl Chloride in Insertion Polymerization (pages 3963–3966)

      Hannes Leicht, Dr. Inigo Göttker-Schnetmann and Prof. Dr. Stefan Mecking

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/anie.201209724

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      A palladium-catalyzed insertion copolymerization of vinyl chloride (VC) and ethylene gave chlorinated polyethylene with CH3CHCl(CH2)n units (see scheme; C blue, O red, Pd orange, S yellow). The CH3CHCl end groups form by 2,1-insertion of VC into palladium hydride complexes, as revealed by detailed labeling studies. This first example of VC incorporation (up to 0.4 mol %) clearly shows that insertion (co)polymerization of VC is in principle feasible.

    23. Photoinduced Electron Transfer

      Synthesis of Highly Substituted Tetrahydrofurans by Catalytic Polar-Radical-Crossover Cycloadditions of Alkenes and Alkenols (pages 3967–3971)

      Jean-Marc M. Grandjean and Prof. David A. Nicewicz

      Version of Record online: 25 FEB 2013 | DOI: 10.1002/anie.201210111

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      Light up my ring: The title reaction is catalyzed by an acridinium/phenylmalononitrile photoredox system. A variety of readily available olefins and unsaturated alcohols can be employed to furnish tetrahydrofuran adducts with complete regiocontrol and up to four contiguous stereogenic centers.

    24. C[BOND]H Functionalization

      Direct Annulations toward Phosphorylated Oxindoles: Silver-Catalyzed Carbon-Phosphorus Functionalization of Alkenes (pages 3972–3976)

      Ya-Min Li, Meng Sun, Hong-Li Wang, Qiu-Ping Tian and Prof. Shang-Dong Yang

      Version of Record online: 25 FEB 2013 | DOI: 10.1002/anie.201209475

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      Silver screen: The AgNO3-catalyzed carbon phosphorylation of alkenes occurs by an alkene addition/cyclization cascade. Ag+ reacts with Ph2P(O)H to form the crucial active intermediate 1, which promotes the reaction. This method requires a cheap, nontoxic silver salt as the catalyst and substrates for the transformation are simple and readily accessible.

    25. C–H Activation

      Carboxylate-Assisted Ruthenium(II)-Catalyzed Hydroarylations of Unactivated Alkenes through C–H Cleavage (pages 3977–3980)

      Dipl.-Chem. Marvin Schinkel, Prof. Dr. Ilan Marek and Prof. Dr. Lutz Ackermann

      Version of Record online: 25 FEB 2013 | DOI: 10.1002/anie.201208446

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      Catalytic: Ruthenium(II)biscarboxylate complexes enabled highly effective hydroarylations of unactivated alkenes through C[BOND]H bond activation. This method has a broad substrate scope and allowed for versatile functionalizations of highly fluorinated alkenes.

    26. Homogeneous Catalysis

      Catalytic Disproportionation of Formic Acid to Generate Methanol (pages 3981–3984)

      Prof. Alexander J. M. Miller, Prof. D. Michael Heinekey, Prof. James M. Mayer and Prof. Karen I. Goldberg

      Version of Record online: 28 FEB 2013 | DOI: 10.1002/anie.201208470

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      The homogeneously catalyzed disproportionation of formic acid to methanol, water, and carbon dioxide is accomplished by only 10 ppm of a readily accessible iridium catalyst, [Cp*Ir(bpy)(H2O)]2+ (Cp*=pentamethylcyclopentadienyl, bpy=2,2′-bipyridine). Methanol is produced under mild, aqueous conditions, without the use of any organic solvents or hydrogen gas.

    27. DNA Nanoparticles

      Use of Single-Site-Functionalized PEG Dendrons To Prepare Gene Vectors that Penetrate Human Mucus Barriers (pages 3985–3988)

      Dr. Anthony J. Kim, Dr. Nicholas J. Boylan, Dr. Jung Soo Suk, Minyoung Hwangbo, Tao Yu, Benjamin S. Schuster, Dr. Liudimila Cebotaru, Dr. Wojciech G. Lesniak, Joon Seok Oh, Pichet Adstamongkonkul, Ashley Y. Choi, Prof. Dr. Rangaramanujam M. Kannan and Prof. Dr. Justin Hanes

      Version of Record online: 4 MAR 2013 | DOI: 10.1002/anie.201208556

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      Mucus-penetrating DNA nanoparticles: A novel synthetic strategy was used to achieve a dense PEG coating on the surface of cationic polymer-based DNA nanoparticles. The dense PEG coating (blue in scheme) endows the nanoparticles with a muco-inert surface, which enables their rapid mucus penetration (trajectory indicated by gray line) and provides efficient gene transfer in various cell types.

    28. Asymmetric Catalysis

      Regio- and Enantioselective Copper(I)-Catalyzed Hydroboration of Borylalkenes: Asymmetric Synthesis of 1,1-Diborylalkanes (pages 3989–3992)

      Xinhui Feng, Heekyung Jeon and Prof. Jaesook Yun

      Version of Record online: 25 FEB 2013 | DOI: 10.1002/anie.201208610

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      A bisphosphine/copper catalyst was used for the asymmetric hydroboration of 1,8-naphthalenediaminatoboryl (Bdan) substituted alkenes (see scheme; pin=pinacolato). Simple alkyl-substituted borylalkenes and styrene derivatives were hydroborated with high regio- and enantioselectivity. The electronic and steric properties of the Bdan group significantly affected the reactivity and regioselectivity of hydroboration.

    29. Nanoparticle Assembly

      Peptide-Directed Synthesis and Assembly of Hollow Spherical CoPt Nanoparticle Superstructures (pages 3993–3995)

      Chengyi Song, Yang Wang and Prof. Nathaniel L. Rosi

      Version of Record online: 6 MAR 2013 | DOI: 10.1002/anie.201209910

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      From “nano” to “super”: Peptide conjugates that consist of cobalt-binding peptides terminated with tails of biphenyl units were used to direct the synthesis and assembly of hollow spherical superstructures of CoPt nanoparticles (see picture). These magnetically separable superstructures exhibit electrocatalytic activity for methanol oxidation.

    30. Nanomaterials

      Carbon Nanotubes Bridged with Graphene Nanoribbons and Their Use in High-Efficiency Dye-Sensitized Solar Cells (pages 3996–3999)

      Zhibin Yang, Mingkai Liu, Chao Zhang, Weng Weei Tjiu, Prof. Tianxi Liu and Prof. Huisheng Peng

      Version of Record online: 11 FEB 2013 | DOI: 10.1002/anie.201209736

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      Tie a ribbon on it: Multiwalled carbon nanotubes were partially unzipped to produce nanoribbons that bridged the nanotubes. The unique structure favors rapid charge transport when used as counter electrodes in dye-sensitized solar cells, resulting in a maximum energy conversion efficiency of 8.23 % versus 7.61 % for a conventional platinum electrode.

    31. Trifluoromethylation

      Alkene Trifluoromethylation Coupled with C[BOND]C Bond Formation: Construction of Trifluoromethylated Carbocycles and Heterocycles (pages 4000–4003)

      Dr. Hiromichi Egami, Ryo Shimizu, Shintaro Kawamura and Prof. Dr. Mikiko Sodeoka

      Version of Record online: 26 FEB 2013 | DOI: 10.1002/anie.201210250

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      The combo pack: Copper-catalyzed trifluoromethylation of alkenes bearing an allylic proton combined with C[BOND]C bond formation affords the title compounds in good to high yields (see scheme). The reactions are faster than allylic trifluoromethylation, especially in 1,4-dioxane. A unique 1,6-oxytrifluoromethylation occurred instead of an anticipated seven-membered ring forming carbotrifluoromethylation reaction.

    32. Asymmetric Catalysis

      Highly Enantioselective [3+2] Annulation of Cyclic Enol Silyl Ethers with Donor–Acceptor Cyclopropanes: Accessing 3a-Hydroxy [n.3.0]Carbobicycles (pages 4004–4007)

      Hao Xu, Jian-Ping Qu, Dr. Saihu Liao, Hu Xiong and Prof. Dr. Yong Tang

      Version of Record online: 4 MAR 2013 | DOI: 10.1002/anie.201300032

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      A new fuse: The title reaction was realized using a new bisoxazoline (BOX)/CuII catalyst. This reaction works well with cyclic enol silyl ethers of different sizes, and can be extended to dienol and benzene-fused substrates, thus providing an effective and general access to a range of 3a-hydroxy [n.3.0]carbobicycles which are found as a core structure in many natural products. TBDPS=tert-butyldiphenylsilyl.

    33. Synthetic Methodology

      Nucleophilic ortho-Propargylation of Aryl Sulfoxides: An Interrupted Pummerer/Allenyl Thio-Claisen Rearrangement Sequence (pages 4008–4011)

      Andrew J. Eberhart and Prof. David J. Procter

      Version of Record online: 27 FEB 2013 | DOI: 10.1002/anie.201300223

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      A new direction: The nucleophilic ortho-propargylation of aryl sulfoxides exploits intermolecular delivery of the nucleophile to sulfur followed by an intramolecular relay to carbon (see scheme). The simple, metal-free procedure is general, regiospecific with regard to the propargyl nucleophile, and completely selective for products of ortho-propargylation over allenylation.

    34. Homogeneous Catalysis

      Direct Synthesis of Pyrroles by Dehydrogenative Coupling of β-Aminoalcohols with Secondary Alcohols Catalyzed by Ruthenium Pincer Complexes (pages 4012–4015)

      Dr. Dipankar Srimani, Yehoshoa Ben-David and Prof. Dr. David Milstein

      Version of Record online: 6 MAR 2013 | DOI: 10.1002/anie.201300574

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      Pyrroles were synthesized in one step by using the acceptorless dehydrogenative coupling of amino alcohols with secondary alcohols (equivalent amounts), catalyzed by ruthenium pincer complexes (0.5 mol %) and a base (less than stoichiometric amounts) through selective C[BOND]N and C[BOND]C bond formation. This atom-economical, environmentally friendly methodology offers easy access to a range of substituted pyrroles in moderate to good yields.

    35. Calcium Catalysis

      Calcium-Catalyzed Cyclopropanation (pages 4016–4019)

      Tobias Haven, Grzegorz Kubik, Stefan Haubenreisser and Prof. Dr. Meike Niggemann

      Version of Record online: 28 FEB 2013 | DOI: 10.1002/anie.201209053

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      No transition metal needed: A calcium-catalyzed cycloisomerization yields highly substituted cyclopropanes with excellent diastereoselectivity (see scheme; Nu=nucleophile, Ts=p-toluenesulfonyl). The reaction is based on the equilibrium of a homoallenyl cation with its cyclopropane congener, which is known for gold-catalyzed reactions. According to mechanistic analysis the carbocation cascade is concerted asynchronous, and hence biomimetic.

    36. Mass Spectrometry of Proteins

      Studying 18 MDa Virus Assemblies with Native Mass Spectrometry (pages 4020–4023)

      Joost Snijder, Dr. Rebecca J. Rose, Dr. David Veesler, Prof. Dr. John E. Johnson and Prof. Dr. Albert J. R. Heck

      Version of Record online: 28 FEB 2013 | DOI: 10.1002/anie.201210197

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      Setting records: Native mass spectometry was used to study the assembly of the 18 MDa capsid of bacteriophage HK97. The previous record for the analysis of capsids by this method was around 10 MDa. The results indicate that the efficiency of desolvation is the main priority in improving native MS instrumentation.

      Corrected by:

      Corrigendum: Corrigendum: Studying 18 MDa Virus Assemblies with Native Mass Spectrometry

      Vol. 53, Issue 12, 3051, Version of Record online: 14 MAR 2014

    37. Surface Chemistry

      Glaser Coupling at Metal Surfaces (pages 4024–4028)

      Dr. Hong-Ying Gao, Dr. Hendrik Wagner, Dr. Dingyong Zhong, Dr. Jörn-Holger Franke, Prof. Dr. Armido Studer and Prof. Dr. Harald Fuchs

      Version of Record online: 19 FEB 2013 | DOI: 10.1002/anie.201208597

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      On-surface synthesis is a promising approach for constructing covalently bound nanostructures. However, the number of reliable chemical reactions suitable for on-surface chemistry is very limited. Arylalkynes can be coupled at various surfaces in a novel 2D Glaser coupling (see picture). This approach can be used for constructing conjugated materials directly on surfaces.

    38. Redox Electronics

      Transistor Functions Based on Electrochemical Rectification (pages 4029–4032)

      Dr. Yaqing Liu, Prof. Bernhard Wolfrum, Martin Hüske, Prof. Andreas Offenhäusser, Prof. Erkang Wang and Dr. Dirk Mayer

      Version of Record online: 4 MAR 2013 | DOI: 10.1002/anie.201207778

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      Golden transistor: A chip-based molecular transistor concept is based on an electrochemical rectifier. The device can perform transistor-like functions with opposite current directions depending on the redox inputs. The unidirectional current recorded at a chemically modified collector electrode can be tuned by the potential applied to an independent generator electrode, which allows switching of the output current and information encoding.

    39. Protein–Lipid Interactions

      In Vivo Profiling and Visualization of Cellular Protein–Lipid Interactions Using Bifunctional Fatty Acids (pages 4033–4038)

      Dr. Per Haberkant, Dr. Reinout Raijmakers, Dr. Marjolein Wildwater, Timo Sachsenheimer, Priv.-Doz. Dr. Britta Brügger, Dr. Kenji Maeda, Dr. Martin Houweling, Dr. Anne-Claude Gavin, Priv.-Doz. Dr. Carsten Schultz, Prof. Gerrit van Meer, Prof. Albert J. R. Heck and Prof. Joost C. M. Holthuis

      Version of Record online: 28 FEB 2013 | DOI: 10.1002/anie.201210178

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      Bifunctional lipid technology: Cells convert externally added photoactivatable and “clickable” fatty acids into a variety of bifunctional phospholipids that can be covalently linked to their protein-binding partners by irradiation with UV light. Derivatization of the clickable group with a reporter molecule makes it possible to identify and image the lipid-bound proteins in situ (see scheme).

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