Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 43

October 18, 2013

Volume 52, Issue 43

Pages 11175–11424

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. Book Review
    7. Highlight
    8. Minireview
    9. Review
    10. Communications
    1. You have full text access to this OnlineOpen article
      Cover Picture: LEGO-NMR Spectroscopy: A Method to Visualize Individual Subunits in Large Heteromeric Complexes (Angew. Chem. Int. Ed. 43/2013) (page 11175)

      Markus Mund, Jan H. Overbeck, Janina Ullmann and Dr. Remco Sprangers

      Version of Record online: 2 OCT 2013 | DOI: 10.1002/anie.201308150

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      Large asymmetric assemblies are difficult to prepare recombinantly and result in complicated NMR spectra that cannot be analyzed in detail. Both issues are addressed simultaneously in the LEGO-NMR method described by R. Sprangers and co-workers in their Communication on page 11401 ff. The method is based on sequential co-expression of NMR active and NMR invisible protein subunits of a large assembly and significantly simplifies both amide backbone and methyl side-chain spectra.

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      Inside Cover: Chemoselective Oxidative C(CO)[BOND]C(methyl) Bond Cleavage of Methyl Ketones to Aldehydes Catalyzed by CuI with Molecular Oxygen (Angew. Chem. Int. Ed. 43/2013) (page 11176)

      Lin Zhang, Prof. Xihe Bi, Xiaoxue Guan, Prof. Xingqi Li, Prof. Qun Liu, Badru-Deen Barry and Dr. Peiqiu Liao

      Version of Record online: 14 OCT 2013 | DOI: 10.1002/anie.201308184

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      The selective oxidative cleavage of C[BOND]C σ-bonds is a great challenge in chemistry and biology. In their Communication on page 11303 ff., X. Bi, Q. Liu, and co-workers describe a novel method for the oxidative C(CO)[BOND]C(α) bond cleavage of ketones that completely terminates at the aldehyde stage. A wide range of aromatic and aliphatic methyl ketones could be transformed into aldehydes with a copper catalyst under an oxygen atmosphere, along with the release of H2 and CO2 as the by-products.

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      Inside Back Cover: Unwrapping Core–Shell Nanowires into Nanoribbon-Based Superstructures (Angew. Chem. Int. Ed. 43/2013) (page 11425)

      Alexander Pevzner, Guy Davidi, Hagit Peretz-Soroka, Ehud Havivi, Dr. Zahava Barkay, Dr. Ronit Popovitz-Biro, Dr. Artium Khatchtourints and Prof. Fernando Patolsky

      Version of Record online: 9 OCT 2013 | DOI: 10.1002/anie.201308312

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      Sacrificial core–shell nanowire precursors can be readily shape-transformed into semiconductor nanoribbon materials by a combination of bottom-up and top-down procedures, as described by F. Patolsky et al. in their Communication on page 11298 ff. This unexpected nanowire-to-nanoribbon transformation process allows the synthesis of superflexible nanoribbons of desired dimension, shape, and chemical composition.

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      Back Cover: Adsorption, Activation, and Dissociation of Oxygen on Doped Oxides (Angew. Chem. Int. Ed. 43/2013) (page 11426)

      Dr. Yi Cui, Dr. Xiang Shao, Dipl.-Chem. Matthias Baldofski, Prof. Joachim Sauer, Dr. Niklas Nilius and Prof. Hans-Joachim Freund

      Version of Record online: 24 SEP 2013 | DOI: 10.1002/anie.201308155

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      The activation of small molecules was thought to be impossible on defect-free wide-band-gap metal oxides owing to their chemical inertness. Based on microscopy and computational results, N. Nilius and co-workers report in their Communication on page 11385 ff. that O2 adsorption on CaO doped with Mo ions leads to the formation of superoxo species with a high propensity for dissociation. Activation takes place through charge transfer from the donor-type Mo ions and proceeds even on ideal surfaces.

  2. Graphical Abstract

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

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. Book Review
    7. Highlight
    8. Minireview
    9. Review
    10. Communications
    1. Rai-Shung Liu (page 11198)

      Version of Record online: 6 MAY 2013 | DOI: 10.1002/anie.201303136

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      “My favorite food is sashimi and Peking duck. If I were not a scientist, I would be a security guard for the National Parks of Taiwan …” This and more about Rai-Shung Liu can be found on page 11406.

  5. Book Review

    1. Top of page
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    6. Book Review
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    9. Review
    10. Communications
    1. Nanomaterials in Catalysis . Edited by Philippe Serp and Karine Philippot. (page 11199)

      Vivek Polshettiwar

      Version of Record online: 22 AUG 2013 | DOI: 10.1002/anie.201305828

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      Wiley-VCH, Weinheim, 2013. 496 pp., hardcover, € 149.00.—ISBN 978-3527331246

  6. Highlight

    1. Top of page
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    3. Graphical Abstract
    4. News
    5. Author Profile
    6. Book Review
    7. Highlight
    8. Minireview
    9. Review
    10. Communications
    1. Single-Molecule Spectroscopy

      Where Does It Vibrate? Raman Spectromicroscopy on a Single Molecule (pages 11202–11204)

      Prof. Dr. J. Michael Gottfried

      Version of Record online: 3 SEP 2013 | DOI: 10.1002/anie.201306405

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      Tip-enhanced Raman spectroscopy combines scanning probe techniques with Raman spectroscopy. Latest developments permit the chemical mapping of individual adsorbed molecules by monitoring molecular vibrations with sub-nanometer resolution. Increased efficiency and reduced photodegradation make this method suitable for studies of adsorbed organic and biomolecules in surface science, catalysis, biochemistry, and related fields.

  7. Minireview

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    9. Review
    10. Communications
    1. Synthetic Methods

      Transition-Metal-Catalyzed Laboratory-Scale Carbon–Carbon Bond-Forming Reactions of Ethylene (pages 11206–11220)

      Vaneet Saini, Dr. Benjamin J. Stokes and Prof. Matthew S. Sigman

      Version of Record online: 17 SEP 2013 | DOI: 10.1002/anie.201303916

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      Functionalize or be functionalized: Ethylene is a valuable reactant for the transition-metal-catalyzed synthesis of a variety of useful small molecules. Examples of some of the latest carbon–carbon bond-forming methods are described, many of which are carried out at ambient temperature and pressure. The outcome is often the incorporation of a synthetically versatile vinyl functional group.

  8. Review

    1. Top of page
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    7. Highlight
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    9. Review
    10. Communications
    1. Heterolytic Fragmentation

      C[BOND]C Fragmentation: Origins and Recent Applications (pages 11222–11251)

      Michael A. Drahl, Prof. Madhuri Manpadi and Prof. Lawrence J. Williams

      Version of Record online: 23 SEP 2013 | DOI: 10.1002/anie.201209833

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      It has been sixty years since Eschenmoser and Frey disclosed the archetypal C[BOND]C fragmentation reaction. New fragmentation reactions that give alkynes and allenes, and variants of the original, have been invented and applied to many complex motifs and natural products.

  9. Communications

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

      Core/Shell Photocatalyst with Spatially Separated Co-Catalysts for Efficient Reduction and Oxidation of Water (pages 11252–11256)

      Dr. Daoai Wang, Dr. Takashi Hisatomi, Dr. Tsuyoshi Takata, Dr. Chengsi Pan, Prof. Masao Katayama, Prof. Jun Kubota and Prof. Kazunari Domen

      Version of Record online: 14 AUG 2013 | DOI: 10.1002/anie.201303693

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      A simple method allows the preparation of core/shell photocatalysts with spatially separated co-catalysts for efficient water splitting. The high activity was attributed to the core/shell structure and separated co-catalysts that assisted separation and collection of the electrons and holes at the respective co-catalysts, owing to active rectification of electron and hole transport (see picture; Eg=2.1 eV).

    2. Synthetic Methods

      Aldehyde-Selective Wacker-Type Oxidation of Unbiased Alkenes Enabled by a Nitrite Co-Catalyst (pages 11257–11260)

      Zachary K. Wickens, Dr. Bill Morandi and Prof. Dr. Robert H. Grubbs

      Version of Record online: 13 SEP 2013 | DOI: 10.1002/anie.201306756

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      Breaking the rules: Reversal of the high Markovnikov selectivity of Wacker-type oxidations was accomplished using a nitrite co-catalyst. Unbiased aliphatic alkenes can be oxidized with high yield and aldehyde selectivity, and several functional groups are tolerated. 18O-labeling experiments indicate that the aldehydic O atom is derived from the nitrite salt.

    3. Mass Spectrometry

      Enhanced Detection of High-Mass Proteins by Using an Active Pixel Detector (pages 11261–11264)

      Dr. Shane R. Ellis, Dr. Julia H. Jungmann, Dr. Donald F. Smith, Dr. Jens Soltwisch and Prof. Dr. Ron M. A. Heeren

      Version of Record online: 3 SEP 2013 | DOI: 10.1002/anie.201305501

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      Flying high: Application of an active pixel detector with high charge sensitivity to a linear time-of-flight mass spectrometer results in enhanced detection of high-mass proteins (such as Immunoglobulin G; IgG) using a conventional microchannel plate detection system. This technique thus provides a means to extend the mass range of such detectors as well as allowing direct visualization of mass-dependent ion-focusing phenomena (see picture).

    4. Polysaccharide Branching

      Nature’s Dendrimer: Characterizing Amylopectin as a Multivalent Host (pages 11265–11268)

      Dr. Sophie R. Beeren and Prof. Ole Hindsgaul

      Version of Record online: 2 SEP 2013 | DOI: 10.1002/anie.201305132

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      Hang on to those branches! Amylopectin, the major polysaccharide of starch, is a predominantly α(1,4)-linked glucan whose properties are defined by its size and the number, distribution, and length of its α(1,6)-linked branches. The amphiphilic probe HPTS-C16H33 binds to terminal helical branches longer than 12 glucose units (green), which allows for a detailed quantitative characterization of polysaccharide branching by 1H NMR spectroscopy.

    5. Natural Product Synthesis

      Enantioselective Total Synthesis of (−)-Minovincine in Nine Chemical Steps: An Approach to Ketone Activation in Cascade Catalysis (pages 11269–11272)

      Brian N. Laforteza, Mark Pickworth and Prof. David W. C. MacMillan

      Version of Record online: 2 SEP 2013 | DOI: 10.1002/anie.201305171

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      Dressed to the nines: The first enantioselective total synthesis of (−)-minovincine has been accomplished in nine chemical steps and 13 % overall yield. A novel, one-step Diels–Alder/β-elimination/conjugate addition organocascade sequence allowed rapid access to the central tetracyclic core in an asymmetric manner. Boc=tert-butoxycarbonyl, LG=leaving group, PMB=para-methoxybenzyl.

    6. Systems Chemistry

      Chemical Signals Turn On Guest Binding through Structural Reconfiguration of Triangular Helicates (pages 11273–11277)

      Anne Sørensen, Dr. Ana M. Castilla, Dr. Tanya K. Ronson, Dr. Michael Pittelkow and Dr. Jonathan R. Nitschke

      Version of Record online: 3 SEP 2013 | DOI: 10.1002/anie.201305245

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      Be my guest: The function of a system based on self-assembled ZnII complexes can be controlled by external chemical stimuli. The complexes are based on a C3-symmetric ligand that forms a unique triangular triple helicate structure 1. Upon subcomponent substitution, 1 is able to transform into a triangular double helicate 2 which, unlike 1, can encapsulate guests.

    7. Virus-Mimetic Gene Transfer

      Virus-Mimetic Cytoplasm-Cleavable Magnetic/Silica Nanoclusters for Enhanced Gene Delivery to Mesenchymal Stem Cells (pages 11278–11281)

      Naveen Gandra, Dong-Dong Wang, Ye Zhu and Prof. Chuanbin Mao

      Version of Record online: 28 AUG 2013 | DOI: 10.1002/anie.201301113

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      It does get in: Phage is made of DNA as a core and protein as a coat, and it can transfer DNA into host cells with high efficiency. Phage-mimetic gene transfer to hard-to-transfect mesenchymal stem cells (MSCs) was achieved using virus-mimetic magnetic silica nanoclusters (VMSNCs). The VMSNCs bear MSC-homing phage-borne protein on the surface and encapsulate DNA inside, promoting the transfer of DNA into MSCs.

    8. Metal–Organic Frameworks

      Formation of a Metal–Organic Framework with High Surface Area and Gas Uptake by Breaking Edges Off Truncated Cuboctahedral Cages (pages 11282–11285)

      Ruirui Yun, Zhiyong Lu, Prof. Yi Pan, Prof. Xiaozeng You and Prof. Junfeng Bai

      Version of Record online: 11 SEP 2013 | DOI: 10.1002/anie.201302715

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      Breaking edges off regular truncated cuboctahedra leads to a metal–organic framework (MOF) with polybenzene topology. This fully characterized MOF with lowest connectivity has the largest BET surface area among interpenetrated MOFs.

    9. Microparticles

      Solvent-Free Synthesis of Microparticles on Superamphiphobic Surfaces (pages 11286–11289)

      Dr. Xu Deng, Maxime Paven, Dr. Periklis Papadopoulos, Dr. Ming Ye, Dr. Si Wu, Thomas Schuster, Dr. Markus Klapper, Dr. Doris Vollmer and Prof. Dr. Hans-Jürgen Butt

      Version of Record online: 5 SEP 2013 | DOI: 10.1002/anie.201302903

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      Polymeric and composite microspheres can be synthesized without solvents or process liquids by using superamphiphobic surfaces. In this method, the repellency of superamphiphobic layers to monomers and polymer melts and the extremely low adhesion to particles are taken advantage of.

    10. Single-Molecule Magnets

      Influence of the Ligand Field on Slow Magnetization Relaxation versus Spin Crossover in Mononuclear Cobalt Complexes (pages 11290–11293)

      Fatemah Habib, Oana R. Luca, Veacheslav Vieru, Muhandis Shiddiq, Dr. Ilia Korobkov, Dr. Serge I. Gorelsky, Dr. Michael K. Takase, Prof. Liviu F. Chibotaru, Prof. Stephen Hill, Prof. Robert H. Crabtree and Prof. Muralee Murugesu

      Version of Record online: 5 SEP 2013 | DOI: 10.1002/anie.201303005

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      The electronic and magnetic properties of the complexes [Co(terpy)Cl2] (1), [Co(terpy)(NCS)2] (2), and [Co(terpy)2](NCS)2 (3) were investigated. The coordination environment around CoII in 1 and 2 leads to a high-spin complex at low temperature and single-molecule magnet properties with multiple relaxation pathways. Changing the ligand field and geometry with an additional terpy ligand leads to spin-crossover behavior in 3 with a gradual transition from high spin to low spin.

    11. Fluorescence Imaging

      Semiconducting Polymer Dots Doped with Europium Complexes Showing Ultranarrow Emission and Long Luminescence Lifetime for Time-Gated Cellular Imaging (pages 11294–11297)

      Dr. Wei Sun, Dr. Jiangbo Yu, Dr. Ruiping Deng, Dr. Yu Rong, Dr. Bryant Fujimoto, Prof. Changfeng Wu, Prof. Hongjie Zhang and Prof. Daniel T. Chiu

      Version of Record online: 12 SEP 2013 | DOI: 10.1002/anie.201304822

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      Bright dots: Semiconducting polymer dots (Pdots) doped with europium complexes possess line-like fluorescence emission, high quantum yield, and long fluorescence lifetime. The Pdots successfully labeled receptors on cells. The long fluorescence lifetime of the Pdots was used to distinguish them from other red fluorescence emitting nanoparticles, and improve the signal-to-noise ratio for time-gated cellular imaging. PVK=poly(9-vinylcarbazole).

    12. Nanostructures

      Unwrapping Core–Shell Nanowires into Nanoribbon-Based Superstructures (pages 11298–11302)

      Alexander Pevzner, Guy Davidi, Hagit Peretz-Soroka, Ehud Havivi, Dr. Zahava Barkay, Dr. Ronit Popovitz-Biro, Dr. Artium Khatchtourints and Prof. Fernando Patolsky

      Version of Record online: 13 SEP 2013 | DOI: 10.1002/anie.201304857

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      A prize for the ribbons: High-quality crystalline semiconducting nanoribbons can be prepared by “unwrapping” core–shell nanowire precursors. For example, Ge nanowires were coated with a Si shell and the top surface was carved by etching whereas the sides were protected by a thin layer of photoresist material. Finally the Ge core was removed selectively by chemical means to give fully opened and flat nanoribbon structures (see picture).

    13. C[BOND]C Bond Cleavage

      Chemoselective Oxidative C(CO)[BOND]C(methyl) Bond Cleavage of Methyl Ketones to Aldehydes Catalyzed by CuI with Molecular Oxygen (pages 11303–11307)

      Lin Zhang, Prof. Xihe Bi, Xiaoxue Guan, Prof. Xingqi Li, Prof. Qun Liu, Badru-Deen Barry and Dr. Peiqiu Liao

      Version of Record online: 2 SEP 2013 | DOI: 10.1002/anie.201305010

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      Aldehyde Termination: A novel copper-catalyzed transformation from methyl ketones into aldehydes has been accomplished. This method is applicable to a wide range of aromatic and aliphatic methyl ketones and chemoselectively produces aldehydes, accompanied by the release of hydrogen (H2) and carbon dioxide (CO2) as by-products.

    14. Carbon Nanotubes

      “Zero-Dimensional” Single-Walled Carbon Nanotubes (pages 11308–11312)

      Dr. Kaladhar Kamalasanan, Dr. Riccardo Gottardi, Dr. Susheng Tan, Dr. Yanan Chen, Dr. Bhaskar Godugu, Dr. Sam Rothstein, Dr. Anna C. Balazs, Dr. Alexander Star and Dr. Steven R. Little

      Version of Record online: 5 SEP 2013 | DOI: 10.1002/anie.201305526

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      The shorter, the more dispersible: An iterative, emulsion-based shortening technique has been used to reduce the length of single-walled carbon nanotubes (SWNTs) to the same order of magnitude as their diameter (ca. 1 nm), thus achieving an effectively “zero-dimensional” structure with improved dispersibility and, after hydroxylation, long-term water solubility. Finally, zero-dimensional SWNTs were positively identified using mass spectrometry for the first time.

    15. Dynamic Hosts

      A Molecular Claw: A Dynamic Cavitand Host (pages 11313–11316)

      Keith Hermann, Mina Nakhla, Judith Gallucci, Erdin Dalkilic, Prof. Arif Dastan and Prof. Jovica D. Badjić

      Version of Record online: 2 SEP 2013 | DOI: 10.1002/anie.201305761

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      Up for grabs: A modular receptor comprises a hexaazatriphenylene “platform” and three imide residues on its concave side carrying flexible alkane chains. The chains not only populate the host's cavity but can also extend and can grab an appropriately sized and shaped guest in solution.

    16. Organocatalysis

      Arylation of Diazoesters by a Transient N[BOND]H Insertion Organocascade (pages 11317–11320)

      Tyler J. Auvil, Sonia S. So and Prof. Dr. Anita E. Mattson

      Version of Record online: 26 AUG 2013 | DOI: 10.1002/anie.201304921

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      It takes two: A unique organocatalyzed cascade for the unsymmetric double arylation of α-nitrodiazoesters is described. This organocascade features the strategic use of carbene-activating anilines in conjunction with a urea catalyst, thus allowing for the synthesis of pharmaceutically attractive α-diarylesters through a transient N[BOND]H insertion process.

    17. Chiral Silanediols in Anion-Binding Catalysis (pages 11321–11324)

      Andrew G. Schafer, Joshua M. Wieting, Dr. Thomas J. Fisher and Prof. Dr. Anita E. Mattson

      Version of Record online: 3 SEP 2013 | DOI: 10.1002/anie.201305496

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      A perfect pair: Silanediols are effective catalysts for the addition of silyl ketene acetals to N-acylisoquinolinium ions. Importantly, this is the first example of a silanediol plausibly participating in anion-binding catalysis, a relatively new direction in the field of hydrogen-bond-donor catalysis. The chiral, enantiopure C2-symmetric silanediol 1 catalyzes enantioselective transformations.

    18. Non-contact Thermometry

      Wide-Range Temperature Sensing using Highly Sensitive Green-Luminescent ZnO and PMMA-ZnO Film as a Non-Contact Optical Probe (pages 11325–11328)

      Satish Laxman Shinde and Prof. Karuna Kar Nanda

      Version of Record online: 12 SEP 2013 | DOI: 10.1002/anie.201302449

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      The heat is on: A variation of green luminescence intensity of ZnO microcrystals embedded in poly(methyl methacrylate) is observed. This material is used for non-contact thermometer, which has an accuracy of 0.1 K over a temperature range of 83–474 K. Scale bars: 10 μm.

    19. Synthetic Methods

      Catalytic Asymmetric β,γ Activation of α,β-Unsaturated γ-Butyrolactams: Direct Approach to β,γ-Functionalized Dihydropyranopyrrolidin-2-ones (pages 11329–11333)

      Dr. Xianxing Jiang, Luping Liu, Panpan Zhang, Yuan Zhong and Prof. Dr. Rui Wang

      Version of Record online: 8 AUG 2013 | DOI: 10.1002/anie.201302622

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      Skeleton in the closet: The title reaction enables the development of the first catalytic β,γ-selective Diels–Alder [4+2] annulation of α,β-unsaturated γ-butyrolactams (see scheme; Boc=tert-butoxycarbonyl, Ts=4-toluenesulfonyl). This process provides a direct method for the enantioselective construction of bi- or tricyclic dihydropyranopyrrolidin-2-one skeletons in only one step.

    20. 2,2′-Azobis(2-methylpropionitrile)-Mediated Alkyne Hydrostannylation: Reaction Mechanism (pages 11334–11338)

      Martins S. Oderinde, Dr. Robert D. J. Froese and Prof. Michael G. Organ

      Version of Record online: 2 SEP 2013 | DOI: 10.1002/anie.201303736

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      Not as radical as you think: The free-radical hydrostannylation of alkynes has been extensively studied and while every published mechanism involves solely radical intermediates, this appears not to be correct. Trace molecular oxygen is necessary for any radical-mediated hydrostannylation to occur with a wide selection of alkynes, thus leading to a proposed hybrid single-electron transfer/radical propagation mechanism. AIBN=2,2′-azobis(2-methylpropionitrile).

    21. Sialic Acids

      Chemical Diversification of Sialic Acid Glycosides by Stereospecific, Chemoselective Deamination (pages 11339–11342)

      Dr. Chandrasekhar Navuluri and Prof. Dr. David Crich

      Version of Record online: 13 SEP 2013 | DOI: 10.1002/anie.201303781

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      Late bloomer: Nitrosation of peracetylated sialic acid glycosides followed by treatment with sodium trifluoroethoxide and then a suitable nucleophile enables the late-stage modification of these glycosides with stereospecific replacement of the acetamido group. This method should enable access to many glycoside derivatives with a minimum of synthetic effort.

    22. C–H Functionalization

      Selective Intermolecular Amination of C[BOND]H Bonds at Tertiary Carbon Centers (pages 11343–11346)

      Prof. Jennifer L. Roizen, David N. Zalatan and Prof.  J. Du Bois

      Version of Record online: 2 SEP 2013 | DOI: 10.1002/anie.201304238

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      C–H insertion: A method for intermolecular amination of tertiary C[BOND]H bonds is described that uses limiting amounts of substrate and a convenient phenol-derived nitrogen source. Structure-selectivity and mechanistic studies suggest that steric interaction between the substrate and active oxidant is the principal determinant of product selectivity.

    23. Catalytic Hydrogenation

      Unexpected Role of Anionic Ligands in the Ruthenium-Catalyzed Base-Free Selective Hydrogenation of Aldehydes (pages 11347–11350)

      Dr. Philippe Dupau, Dr. Lucia Bonomo and Laurent Kermorvan

      Version of Record online: 3 SEP 2013 | DOI: 10.1002/anie.201304912

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      Bigger and better: The replacement of anionic chloride ligands in Noyori-type [(diamine)(diphosphine)RuCl2] catalysts with bulky carboxylate ligands enabled the efficient selective hydrogenation of a variety of aldehydes under base-free conditions (see scheme). Turnover numbers of up to 100 000 were reached in the presence of a bulky carboxylic acid co-catalyst. This type of catalytic system probably operates through an inner-sphere mechanism.

    24. Organocatalysis

      Alkoxide Activation of Aminoboranes towards Selective Amination (pages 11351–11355)

      Cristina Solé and Dr. Elena Fernández

      Version of Record online: 3 SEP 2013 | DOI: 10.1002/anie.201305098

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      Piece of the (inter)action: The interaction of alkoxides with the sp2 Bpin (pin=pinacol) moiety in aminoboranes forms the in situ Lewis acid–base adduct [RO[RIGHTWARDS ARROW]B(OR)2[BOND]N(R′)2] which enables the amino moiety to react as a strong nucleophile with several electrophiles, thus providing amino alcohols, β-enamino esters, and β-hydroxy amides in a direct and remarkably selective way (see scheme).

    25. Multiple Bonds

      Alkene to Carbyne: Tandem Lewis Acid Activation and Dehydrogenation of a Molybdenum Ethylene Complex (pages 11356–11359)

      Tom E. Stennett, Dr. Mairi F. Haddow and Prof. Dr. Duncan F. Wass

      Version of Record online: 27 AUG 2013 | DOI: 10.1002/anie.201305233

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      Carbyne formation: Treatment of a molybdenum ethylene complex with B(C6F5)3 induces ditopic activation of an ethylene ligand and acceptor-assisted ethane elimination to generate a novel type of zwitterionic carbyne complex (see scheme).

    26. Paint Degradation

      Nanoscale Investigation of the Degradation Mechanism of a Historical Chrome Yellow Paint by Quantitative Electron Energy Loss spectroscopy Mapping of Chromium Species (pages 11360–11363)

      Haiyan Tan, He Tian, Prof. Jo Verbeeck, Letizia Monico, Prof. Koen Janssens and Prof. Gustaaf Van Tendeloo

      Version of Record online: 13 SEP 2013 | DOI: 10.1002/anie.201305753

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      Getting the picture: The investigation of 100 year old chrome yellow paint by transmission electron microscopy and spectroscopy has led to the identification of four types of core–shell particles. This nanoscale investigation has allowed a mechanism to be proposed for the darkening of some bright yellow colors in Van Gogh's paintings (e.g. in Falling leaves (Les Alyscamps), 1888).

    27. Chemical Logic Gates

      Cascading of Molecular Logic Gates for Advanced Functions: A Self-Reporting, Activatable Photosensitizer (pages 11364–11368)

      Dr. Sundus Erbas-Cakmak and Prof. Dr. Engin U. Akkaya

      Version of Record online: 12 SEP 2013 | DOI: 10.1002/anie.201306177

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      Logical progress: Independent molecular logic gates have been designed and characterized. Then, the individual molecular logic gates were coerced to work together within a micelle. Information relay between the two logic gates was achieved through the intermediacy of singlet oxygen. Working together, these concatenated logic gates result in a self-reporting and activatable photosensitizer. GSH=glutathione.

    28. Cyclization Reactions

      Rhodium(I)-Catalyzed Cycloisomerization of Alkene-Substituted Allenylcyclopropanes: Stereoselective Formation of Bicyclo[4.3.0]nonadienes (pages 11369–11372)

      Katsuya Sugikubo, Fukiko Omachi, Yuuki Miyanaga, Dr. Fuyuhiko Inagaki, Chiaki Matsumoto and Prof. Dr. Chisato Mukai

      Version of Record online: 2 SEP 2013 | DOI: 10.1002/anie.201305958

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      A productive channel for pent-up energy: The [{RhCl(CO)2}2]-catalyzed ring-opening of both E and Z 1-cyclopropylocta-1,2,6-trienes exclusively produced cis-4,5-dimethylbicyclo[4.3.0]nona-1(9),2-dienes with three contiguous stereogenic centers. When this transformation was applied to the 1,2,7-triene double-bond isomers, the same products were formed in a completely stereoselective manner (see scheme).

    29. Natural Product Synthesis

      Divergent and Efficient Syntheses of the Lycopodium Alkaloids (−)-Lycojaponicumin C, (−)-8-Deoxyserratinine, (+)-Fawcettimine, and (+)-Fawcettidine (pages 11373–11376)

      Si-Hua Hou, Prof. Dr. Yong-Qiang Tu, Lin Liu, Prof. Dr. Fu-Min Zhang, Prof. Dr. Shao-Hua Wang and Dr. Xiao-Ming Zhang

      Version of Record online: 2 SEP 2013 | DOI: 10.1002/anie.201306369

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      Four from one: The four title alkaloids (structures shown in blue box) have been synthesized by using a common versatile intermediate with a 6/5/5 tricyclic skeleton. This tricyclic intermediate could be easily assembled by using an intramolecular carbene addition/cyclization and a Dieckmann condensation/Tsuji–Trost allylation as key steps.

    30. Asymmetric Synthesis

      A General Strategy for the Synthesis of P-Stereogenic Compounds (pages 11377–11380)

      Dr. Olivier Berger and Prof. Jean-Luc Montchamp

      Version of Record online: 9 SEP 2013 | DOI: 10.1002/anie.201306628

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      A great leap forward toward the general synthesis of P-stereogenic compounds: Heating H3PO2 with (−)-menthol and paraformaldehyde gives easily crystallized menthyl hydroxymethyl-H-phosphinate (1). From this product, virtually any P-stereogenic compound can be synthesized (see picture).

    31. C[BOND]H activation

      Methane Coupling over Magnesium Oxide: How Doping Can Work (pages 11381–11384)

      Pierre Schwach, Dr. Marc Georg Willinger, Dr. Annette Trunschke and Prof. Dr. Robert Schlögl

      Version of Record online: 17 SEP 2013 | DOI: 10.1002/anie.201305470

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      Electronic doping of magnesium oxide catalysts has an effect on the oxidative coupling of methane. Highly active sites can be created by co-modification of MgO with iron and gold in ppm quantities.

    32. Oxygen Activation

      Adsorption, Activation, and Dissociation of Oxygen on Doped Oxides (pages 11385–11387)

      Dr. Yi Cui, Dr. Xiang Shao, Dipl.-Chem. Matthias Baldofski, Prof. Joachim Sauer, Dr. Niklas Nilius and Prof. Hans-Joachim Freund

      Version of Record online: 17 SEP 2013 | DOI: 10.1002/anie.201305119

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      Charge transfer in the presence of dopants is relevant for the adorption and activation of small molecules, such as O2. Scanning tunneling microscopy and DFT calculations provide evidence for the formation of strongly bound superoxo species on chemically inert, Mo-doped CaO films (see picture). This oxygen surface species shows a high propensity to dissociate. Dopants could also be important for the activation of hydrocarbons on inert oxides.

    33. Gold Complexes

      β- and α-Hydride Abstraction in Gold(I) Alkyl Complexes (pages 11388–11391)

      Gaël Ung and Prof. Guy Bertrand

      Version of Record online: 11 SEP 2013 | DOI: 10.1002/anie.201306550

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      Why not both? Both β- and α-hydrogen atoms of gold alkyl complexes are hydridic enough to be abstracted, opening a new route to gold–alkene and gold–carbene complexes, respectively.

    34. Carbenes

      Synthesis and Reactivity of Metal Complexes with Acyclic (Amino)(Ylide)Carbene Ligands (pages 11392–11395)

      Elisa González-Fernández, Jörg Rust and Dr. Manuel Alcarazo

      Version of Record online: 3 SEP 2013 | DOI: 10.1002/anie.201305311

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      No cycle required: The straightforward synthesis of acyclic (amino)(ylide)carbene gold complexes was achieved by reaction of isocyanide gold complexes with phosphorus and arsenic ylides as well as electron-rich olefins. Their ability to form bimetallic species and to act as ligand-transfer reagents has also been established.

    35. C[BOND]C Coupling

      Nitrile–Nitrile C[BOND]C Coupling at Group 4 Metallocenes to Form 1-Metalla-2,5-diaza-cyclopenta-2,4-dienes: Synthesis and Reactivity (pages 11396–11400)

      Dipl.-Chem. Lisanne Becker, Dr. Perdita Arndt, Dr. Haijun Jiao, Dr. Anke Spannenberg and Prof. Dr. Uwe Rosenthal

      Version of Record online: 11 SEP 2013 | DOI: 10.1002/anie.201303748

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      The C[BOND]C coupling of aryl nitriles at Group 4 metallocenes leads to unusual ring-strained 1-metalla-2,5-diaza-cyclopenta-2,4-dienes. The structural, energetic, and chemical properties of these complexes are described. The reactions of these compounds towards CH3CN, H2, CO2, and HCl usually lead to the release of one nitrile and its replacement by different co-substrates.

    36. Protein NMR Spectroscopy

      You have full text access to this OnlineOpen article
      LEGO-NMR Spectroscopy: A Method to Visualize Individual Subunits in Large Heteromeric Complexes (pages 11401–11405)

      Markus Mund, Jan H. Overbeck, Janina Ullmann and Dr. Remco Sprangers

      Version of Record online: 14 AUG 2013 | DOI: 10.1002/anie.201304914

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      Seeing the big picture: Asymmetric macromolecular complexes that are NMR active in only a subset of their subunits can be prepared, thus decreasing NMR spectral complexity. For the hetero heptameric LSm1–7 and LSm2–8 rings NMR spectra of the individual subunits of the complete complex are obtained, showing a conserved RNA binding site. This LEGO-NMR technique makes large asymmetric complexes accessible to detailed NMR spectroscopic studies.

    37. Organometallic B12 Chemistry

      Phenylethynylcobalamin: A Light-Stable and Thermolysis-Resistant Organometallic Vitamin B12 Derivative Prepared by Radical Synthesis (pages 11406–11409)

      Dr. Markus Ruetz, Robert Salchner, Dr. Klaus Wurst, Dr. Sergey Fedosov and Prof. Dr. Bernhard Kräutler

      Version of Record online: 12 SEP 2013 | DOI: 10.1002/anie.201305206

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      Don't take this antivitamin! 2-Phenylethynylcobalamin (see picture) was prepared in a newly developed radical reaction using cob(II)alamin and 1-iodo-2-phenylethyne. It has an exceptionally short organometallic bond and is a remarkably light-stable and heat-resistant organometallic cobalamin. It is bound well by two important proteins of the human B12 transport system and has properties that are as expected for a new type of an “antivitamin B12”.

    38. NMR Spectroscopy

      Predicting the Rotational Tumbling of Dynamic Multidomain Proteins and Supramolecular Complexes (pages 11410–11414)

      Dr. Nasrollah Rezaei-Ghaleh, Frederik Klama, Dr. Francesca Munari and Prof. Dr. Markus Zweckstetter

      Version of Record online: 2 SEP 2013 | DOI: 10.1002/anie.201305094

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      Time is of the essence: The rotational motion of biomolecules depends on intra- and intermolecular interactions and thus on distinct functional states. A new method, called HYCUD accurately predicts rotational correlation times in complex dynamic systems. It gives insights into the motional behavior of multidomain proteins in their free form and in supramolecular complexes.

    39. Zirconocene Hydrido Complexes

      Facile Access to Tuneable Schwartz’s Reagents: Oxidative Addition Products from the Reaction of Amide N[BOND]H Bonds with Reduced Zirconocene Complexes (pages 11415–11419)

      Dipl.-Chem. Martin Haehnel, B. Sc. Jacky C.-H. Yim, Prof. Dr. Laurel L. Schafer and Prof. Dr. Uwe Rosenthal

      Version of Record online: 3 SEP 2013 | DOI: 10.1002/anie.201305246

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      On the tracks of Schwartz's reagent: Two zirconocene hydrido amidate complexes are synthesized by formal oxidative addition of amide N[BOND]H bonds to reduced zirconocene fragments. Insertion reactions with alkenes show a different behavior than Schwartz's reagent by forming branched insertion products. The insertion product and the hydrido complex are characterized by X-ray analysis.

    40. Water Reduction

      Water Reduction with Visible Light: Synergy between Optical Transitions and Electron Transfer in Au-TiO2 Catalysts Visualized by In situ EPR Spectroscopy (pages 11420–11424)

      Jacqueline B. Priebe, Dr. Michael Karnahl, Dr. Henrik Junge, Prof. Dr. Matthias Beller, Dr. Dirk Hollmann and Prof. Dr. Angelika Brückner

      Version of Record online: 12 SEP 2013 | DOI: 10.1002/anie.201306504

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      Golden electrons: Visible light excites conduction electron transfer from gold particles to support vacancies where they are taken up by protons to produce hydrogen. This transfer process was visualized by in situ EPR spectroscopy.

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