Angewandte Chemie International Edition

Cover image for Vol. 51 Issue 41

October 8, 2012

Volume 51, Issue 41

Pages 10197–10416

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Addition
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Cover Picture: Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal–Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts (Angew. Chem. Int. Ed. 41/2012) (page 10197)

      Dawei Feng, Dr. Zhi-Yuan Gu, Dr. Jian-Rong Li, Dr. Hai-Long Jiang, Zhangwen Wei and Prof. Dr. Hong-Cai Zhou

      Article first published online: 31 AUG 2012 | DOI: 10.1002/anie.201206772

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      Acid-resistant, water-stable MOFs with ultra-large 1D channels exhibiting biomimetic catalytic activity have been developed. In their Communication on page 10307 ff., H.-C. Zhou and co-workers report the synthesis, characterization, and catalytic studies of an isostructural series of MOFs designated as PCN-222. The combination of a zirconium cluster and an iron–porphyrin derivative gave rise to PCN-222(Fe), which is highly effective in catalyzing the oxidation of a number of peroxidase substrates.

    2. You have free access to this content
      Inside Cover: Genetic Incorporation of a Metal-Chelating Amino Acid as a Probe for Protein Electron Transfer (Angew. Chem. Int. Ed. 41/2012) (page 10198)

      Xiaohong Liu, Jiasong Li, Jianshu Dong, Cheng Hu, Weimin Gong and Jiangyun Wang

      Article first published online: 7 SEP 2012 | DOI: 10.1002/anie.201206874

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      Probing electron-transfer reactions in green fluorescent protein (GFP) was aided by the incorporation of a metal-chelating tyrosine derivative, pyTyr. In their Communication on page 10261 ff., W. M. Gong, J. Y. Wang et al. report that photoinduced electron transfer between the pyTyr-bound CuII ion and the GFP chromophore was distance-dependent and occurred on the nanosecond timescale.

    3. You have free access to this content
      Inside Back Cover: Intermolecular Oxidative Annulation of 2-Aminoanthracenes to Diazaacenes and Aza[7]helicenes (Angew. Chem. Int. Ed. 41/2012) (page 10417)

      Kiyohiko Goto, Ryuichi Yamaguchi, Dr. Satoru Hiroto, Hiroshi Ueno, Prof. Dr. Tsuyoshi Kawai and Prof. Dr. Hiroshi Shinokubo

      Article first published online: 24 SEP 2012 | DOI: 10.1002/anie.201207155

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      In the 19th century F. F. Runge synthesized a black material through the oxidation of aniline. This substance was named “aniline black” by W. H. Perkin, and is now a well-known black dye. In their Communication on page 10333 ff., H. Shinokubo et al. discuss a novel aspect of this reaction of aromatic amines, namely the selective formation of diazaacenes and azahelicenes from aminoanthracene derivatives. The product distribution can be effectively controlled by the reaction conditions.

    4. You have free access to this content
      Back Cover: Observation of Subcellular Metabolite Gradients in Single Cells by Laser Ablation Electrospray Ionization Mass Spectrometry (Angew. Chem. Int. Ed. 41/2012) (page 10418)

      Jessica A. Stolee, Dr. Bindesh Shrestha, Getachew Mengistu and Prof. Akos Vertes

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201206834

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      Combining cell microdissection with laser ablation electrospray ionization (LAESI) mass spectrometry enables the metabolic profiling of subcellular compartments, as shown by A. Vertes and co-workers in their Communication on page 10386 ff. The use of LAESI mass spectrometry allowed the dissected cell to be studied in its natural tissue-embedded state. Large metabolite gradients between the nucleus and the cytoplasm were revealed and over 30 metabolites were detected in a large cell compartment, for example the nucleus.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Addition
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 41/2012 (pages 10201–10214)

      Article first published online: 1 OCT 2012 | DOI: 10.1002/anie.201290070

  3. Addition

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Addition
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Addition: Reaction of Frustrated Lewis Pairs with Conjugated Ynones-Selective Hydrogenation of the Carbon–Carbon Triple Bond (page 10213)

      Dr. Bao-Hua Xu, Dr. Gerald Kehr, Dr. Roland Fröhlich, Birgit Wibbeling, Birgitta Schirmer, Prof. Dr. Stefan Grimme and Prof. Dr. Gerhard Erker

      Article first published online: 1 OCT 2012 | DOI: 10.1002/anie.201206415

      This article corrects:
  4. Corrigendum

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Addition
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Corrigendum: The Benzyne Aza-Claisen Reaction (page 10214)

      Alastair A. Cant, Guillaume H. V. Bertrand, Jaclyn L. Henderson, Lee Roberts and Michael F. Greaney

      Article first published online: 1 OCT 2012 | DOI: 10.1002/anie.201206624

      This article corrects:

      The Benzyne Aza-Claisen Reaction1

      Vol. 48, Issue 28, 5199–5202, Article first published online: 12 JUN 2009

  5. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Addition
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. Chengde Mao (page 10220)

      Article first published online: 21 JUN 2012 | DOI: 10.1002/anie.201203437

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      “My motto is ‘simple is beautiful’. My favorite drink is green tea …” This and more about Chengde Mao can be found on page 10220.

  7. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. Addition
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. Genentech. The Beginnings of Biotech. By Sally Smith Hughes. (page 10222)

      Ernst-Ludwig Winnacker

      Article first published online: 20 SEP 2012 | DOI: 10.1002/anie.201206934

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      University of Chicago Press, 2011. 232 pp., hardcover, $ 25.00.—ISBN 978-0226359182

  9. Highlights

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

      Intramolecular Alkoxycyanation and Alkoxyacylation Reactions: New Types of Alkene Difunctionalizations for the Construction of Oxygen Heterocycles (pages 10224–10225)

      Prof. Dr. John P. Wolfe

      Article first published online: 5 SEP 2012 | DOI: 10.1002/anie.201204470

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      Functionalized dihydrobenzofuran derivatives can be obtained by intramolecular alkoxycyanation and alkoxyacylation of alkenes (see scheme). In both transformations, selective activation of an O[BOND]FG bond is accomplished by using a transition-metal catalyst. These transformations represent a conceptually new approach to metal-catalyzed alkene difunctionalization.

    2. Molecular Motors

      And Yet It Rotates: The Starter for a Molecular Wankel Motor (pages 10226–10227)

      Prof. Dr. Gabriel Merino and Prof. Dr. Thomas Heine

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201206188

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      Gentlemen, start your engines! A starter system for the smallest molecular motor known so far, B13+, has been prepared. An external laser field of circular polarized light with a tuned frequency is used to trigger the rotation of the inner and outer rings of the planar π-aromatic double-ring system (see picture). Can this idea be transferred to other systems in nanotechnology?

  10. Minireview

    1. Top of page
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    3. Graphical Abstract
    4. Addition
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. Coordination Chemistry

      Redox-Active Ligands in Catalysis (pages 10228–10234)

      Dr. Vijayendran K. K. Praneeth, Dr. Mark R. Ringenberg and Prof. Thomas R. Ward

      Article first published online: 20 SEP 2012 | DOI: 10.1002/anie.201204100

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      Juggling with both hands: For sustainable energy, mastering multi-electron catalytic processes is the key feature. To address this challenge, nature combines redox-active metals with redox-active mediators or ligands. The resulting catalytic transformations (e.g. water splitting, CO2 reduction, C[BOND]H activation) proceed with low kinetic barriers. This Minireview highlights recent examples of homogeneous catalysis involving redox-active ligands.

  11. Review

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    11. Minireview
    12. Review
    13. Communications
    1. C[BOND]H Activation

      Beyond Directing Groups: Transition-Metal-Catalyzed C[BOND]H Activation of Simple Arenes (pages 10236–10254)

      Nadine Kuhl, Dr. Matthew N. Hopkinson, Dr. Joanna Wencel-Delord and Prof. Dr. Frank Glorius

      Article first published online: 20 SEP 2012 | DOI: 10.1002/anie.201203269

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      Directionless? Obtaining high levels of reactivity and selectivity is crucial for extending the scope of modern C[BOND]H activation chemistry. Whereas most of these transformations rely on the help of directing groups (DGs; leading to ortho-functionalized products and a remaining DG), the development of powerful alternative strategies is of utmost importance. Progress and trends of this evolving field are discussed.

  12. Communications

    1. Top of page
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    3. Graphical Abstract
    4. Addition
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Book Review
    10. Highlights
    11. Minireview
    12. Review
    13. Communications
    1. Photobiophysics

      Absorption by Isolated Ferric Heme Nitrosyl Cations In Vacuo (pages 10256–10260)

      Dr. Jean Ann Wyer and Prof. Steen Brøndsted Nielsen

      Article first published online: 10 SEP 2012 | DOI: 10.1002/anie.201206213

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      Almost innocent: In photobiophysical studies of ferric heme nitrosyl complexes, the absorption spectra of six-coordinate complexes with NO and Met or Cys are similar to that of the five-coordinate complex ion Fe(heme)(NO)+. Since the absorption spectra of related proteins with histidine as the proximal ligand are similar to those of the gaseous complexes, the protein microenvironment has little effect on the lowest-energy transition of the porphyrin macrocycle.

    2. Metalloprotein Engineering

      Genetic Incorporation of a Metal-Chelating Amino Acid as a Probe for Protein Electron Transfer (pages 10261–10265)

      Xiaohong Liu, Jiasong Li, Jianshu Dong, Cheng Hu, Weimin Gong and Jiangyun Wang

      Article first published online: 31 AUG 2012 | DOI: 10.1002/anie.201204962

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      ET encounters jellyfish: Through the incorporation of the metal-chelating amino acid pyTyr into green fluorescent protein (GFP) from jellyfish, photoinduced electron transfer (ET) from the GFP chromophore to a bound CuII ion was shown to occur within one nanosecond in a distance-dependent manner. The crystal structure of GFP with pyTyr at a specific position shows the structural basis for the nanomolar binding affinity of pyTyr to CuII ions.

    3. Bimetallic Nanocrystals

      Synthesis of Pd-Rh Core–Frame Concave Nanocubes and Their Conversion to Rh Cubic Nanoframes by Selective Etching of the Pd Cores (pages 10266–10270)

      Shuifen Xie, Dr. Ning Lu, Prof. Zhaoxiong Xie, Dr. Jinguo Wang, Prof. Moon J. Kim and Prof. Younan Xia

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201206044

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      The art of addition and subtraction: By confining the nucleation and growth of Rh atoms only to the corners and edges of Pd cubic seeds, Pd-Rh core–frame nanocrystals were obtained with concave side faces. The Pd cores were then selectively removed by oxidative etching to generate Rh cubic nanoframes with a highly open structure (see picture).

    4. Asymmetric Catalysis

      Organocatalytic Activation of Polycyclic Aromatic Compounds for Asymmetric Diels–Alder Reactions (pages 10271–10274)

      Dr. Hao Jiang, Dr. Carles Rodríguez-Escrich, Tore Kiilerich Johansen, Dr. Rebecca L. Davis and Prof. Karl Anker Jørgensen

      Article first published online: 13 SEP 2012 | DOI: 10.1002/anie.201205836

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      The anglerfish catalyst: The activation of anthracenes through aminocatalysis (see scheme) allows them to undergo [4+2] cycloadditions with concomitant breaking of the aromaticity at room temperature and low catalyst loadings. A highly enantioselective Diels–Alder reaction of anthracenes has been developed using nitroalkenes as dienophiles.

    5. Synthetic Methods

      Rhodium-Catalyzed Cross-Aldol Reaction: In Situ Aldehyde-Enolate Formation from Allyloxyboranes and Primary Allylic Alcohols (pages 10275–10279)

      Luqing Lin, Kumiko Yamamoto, Dr. Shigeki Matsunaga and Prof. Dr. Motomu Kanai

      Article first published online: 13 SEP 2012 | DOI: 10.1002/anie.201205680

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      Dip in! A Rh/dippf catalyst generates aldehyde-derived enol boranes at ambient temperature by isomerization of allyloxy- and homoallyloxyboranes. A one-pot isomerization/cross-aldol sequence provides aldehyde–aldehyde adducts in good yield with syn selectivity. Direct use of primary allylic and homoallylic alcohols was also achieved.

    6. Molecular Diversity

      Efficient Assembly of Iminodicarboxamides by a “Truly” Four-Component Reaction (pages 10280–10283)

      Kareem Khoury, Dr. Mantosh K. Sinha, Dr. Tadamichi Nagashima, Eberhardt Herdtweck and Prof. Alexander Dömling

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201205366

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      Mix and match: Similar to a galaxy consisting of millions of stars, a multicomponent reaction (MCR) system can result in millions of compounds. The MCR of α-amino acids, oxo components, isocyanides, and amines leads to numerous and diverse compounds, thus having enormous potential for drug discovery or catalyst screening.

      Corrected by:

      Corrigendum: Corrigendum: Efficient Assembly of Iminodicarboxamides by a “Truly” Four-Component Reaction

      Vol. 52, Issue 21, 5425, Article first published online: 10 MAY 2013

    7. Adsorption

      An MoSx Structure with High Affinity for Adsorbate Interaction (pages 10284–10288)

      Dr. Dezheng Sun, M. Sc. Wenhao Lu, Dr. Duy Le, M. Sc. Quan Ma, M. Sc. Maral Aminpour, Dr. Marisol Alcántara Ortigoza, Sarah Bobek, M. Sc. John Mann, M. Sc. Jonathan Wyrick, Dr. Talat S. Rahman and Dr. Ludwig Bartels

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201205258

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      An Mo2S3 monolayer grown on copper coexists with well-known MoS2 patches and triangular islands. Imaging by scanning tunneling microscopy after exposure to anthraquinone shows the new structure to be far more active in adsorption, permitting even the formation of a compressed adsorbate layer before other surface areas, including the supposedly reactive brim areas of MoS2 islands, capture this adsorbate.

    8. Solid-State NMR

      Hydrogen Bonding in Alzheimer’s Amyloid-β Fibrils Probed by 15N{17O} REAPDOR Solid-State NMR Spectroscopy (pages 10289–10292)

      Prof. Oleg N. Antzutkin, Dr. Dinu Iuga, Dr. Andrei V. Filippov, Robert T. Kelly, Dr. Johanna Becker-Baldus, Prof. Steven P. Brown and Prof. Ray Dupree

      Article first published online: 13 SEP 2012 | DOI: 10.1002/anie.201203595

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      An exclusive label: 15N{17O} REAPDOR NMR was used to validate intermolecular C[DOUBLE BOND]17O⋅⋅⋅H[BOND]15N hydrogen bonding in Ac-Aβ(16–22)-NH2 (see scheme) and Aβ(11–25) amyloid fibrils, which are associated with Alzheimer's disease, by selectively labeling them with 17O and 15N. This method was effective for confirming the structure of these fibrils, and could be useful for a number of other biological samples.

    9. Bacterial Alkaloids

      Bacterial Synthesis of Diverse Indole Terpene Alkaloids by an Unparalleled Cyclization Sequence (pages 10293–10297)

      Dr. Zhongli Xu, Martin Baunach, Dr. Ling Ding and Prof. Dr. Christian Hertweck

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201204087

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      Getting indole terpenes into shape: Genetic analysis, pathway dissection, and heterologous reconstitution provide first insights into bacterial indolosesquiterpenoid biosynthesis and unveil the involvement of a new type of terpene cyclase and an indole oxygenase in the formation of indosespene, xiamycin, and sespenine ring systems. Furthermore, heterologous pathway expression led to the discovery of C[BOND]C- and C[BOND]N-linked xiamycin dimers.

    10. Peptide Cyclization

      Cyclization of Peptides by using Selenolanthionine Bridges (pages 10298–10302)

      Dr. Aline Dantas de Araujo, Dr. Mehdi Mobli, Prof. Glenn F. King and Prof. Paul F. Alewood

      Article first published online: 18 SEP 2012 | DOI: 10.1002/anie.201204229

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      Selenocysteine does the job: Lanthionine bridges are important structural elements in naturally occurring lantibiotics. They can be engineered into peptides to increase biological activity and metabolic stability. Macrocyclization of peptides by intramolecular thiolation of cysteine is often difficult but can be achieved by replacing cysteine with the more reactive isosteric selenocysteine amino acid.

    11. DNA Nanostructures

      Fabrication of ssDNA/Oligo(ethylene glycol) Monolayers and Complex Nanostructures by an Irradiation-Promoted Exchange Reaction (pages 10303–10306)

      M. Nuruzzaman Khan, Vinalia Tjong, Prof. Ashutosh Chilkoti and Prof. Dr. Michael Zharnikov

      Article first published online: 17 SEP 2012 | DOI: 10.1002/anie.201204245

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      Creative design: An approach to preparing mixed monolayers of thiolated single-stranded DNA (ssDNA) and oligo(ethylene glycol)s (OEG-AT) in a broad range of compositions as well as ssDNA/OEG-AT patterns of any required shape (see top figure) has been shown. A combination of this approach with surface-initiated enzymatic polymerization allows complex 3D DNA nanostructures to be sculpted with high spatial precision (bottom).

    12. Porous Coordination Networks

      Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal–Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts (pages 10307–10310)

      Dawei Feng, Dr. Zhi-Yuan Gu, Dr. Jian-Rong Li, Dr. Hai-Long Jiang, Zhangwen Wei and Prof. Dr. Hong-Cai Zhou

      Article first published online: 21 AUG 2012 | DOI: 10.1002/anie.201204475

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      Biomimetic MOF: Extremely stable MOFs with different open metal sites and ultra-large 1D channels, PCN-222 (Fe, Mn, Co, Ni, Cu, and Zn), have been assembled with eight-connected Zr6 clusters and redox-active metalloporphyrin motifs. PCN-222(Fe) shows peroxidase-like activity in aqueous solution, exhibiting highly effective biomimetic oxidation on a number of substrates.

    13. Visualization of Electrodes

      4D Visualization of a Cathode Catalyst Layer in a Polymer Electrolyte Fuel Cell by 3D Laminography–XAFS (pages 10311–10314)

      Dr. Takahiro Saida, Dr. Oki Sekizawa, Nozomu Ishiguro, Dr. Masato Hoshino, Dr. Kentaro Uesugi, Prof. Dr. Tomoya Uruga, Prof. Dr. Shin-ichi Ohkoshi, Prof. Dr. Toshihiko Yokoyama and Prof. Dr. Mizuki Tada

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201204478

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      Four-dimensional visualization of Pt/C cathode catalyst layers in membrane electrode assemblies (MEAs) were successfully performed by a newly developed method, namely laminography–XAFS (X-ray absorption fine structure). The method not only enables imaging of the 3D distribution of Pt nanoparticle cathode catalysts, but also the chemical states of the Pt catalysts in fresh and degraded MEAs in a nondestructive manner.

    14. Nanotechnology

      Creation of Pure Nanodrugs and Their Anticancer Properties (pages 10315–10318)

      Dr. Hitoshi Kasai, Dr. Tatsuya Murakami, Yoshikazu Ikuta, Yoshitaka Koseki, Dr. Koichi Baba, Prof. Hidetoshi Oikawa, Prof. Hachiro Nakanishi, Dr. Masahiro Okada, Mitsuru Shoji, Prof. Minoru Ueda, Prof. Hiroshi Imahori and Prof. Mitsuru Hashida

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201204596

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      A method for preparing nanoparticles of a water-insoluble drug that are suitable for administration to the human body has been established. A reprecipitation method was used to fabricate 50 nm nanoparticles of dimerized SN-38, an anticancer camptothecin derivative, that form stable aqueous dispersions and can penetrate into cancer cells to inhibit cell proliferation more potently than irinotecan.

    15. Crystal Engineering

      Elastic and Bendable Caffeine Cocrystals: Implications for the Design of Flexible Organic Materials (pages 10319–10323)

      Soumyajit Ghosh and Prof. Dr. C. Malla Reddy

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201204604

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      Crystalline spring: Single crystals formed from caffeine, 4-chloro-3-nitrobenzoic acid, and methanol (1:1:<1) have an interlocked structure with weak interactions in the three perpendicular directions, as well as solvent channels, and display reversible elastic bending. Excellent conservation of long-range order even after many bending cycles is observed, thus demonstrating the opportunities for flexible organic materials.

    16. Self-Cleaning Materials

      Self-Cleaning Functional Molecular Materials (pages 10324–10328)

      M. B. Avinash, Elisabeth Verheggen, Prof. Dr. Carsten Schmuck and Dr. T. Govindaraju

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201204608

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      Clean and polish: The spontaneous hierarchical molecular assembly of a naphthalenediimide derivative is used to form microarrays by a simple solution-processing technique. This method is further employed to fabricate a self-cleaning surface with very low slide angle (3°) and contact angle hysteresis (1°).

    17. Photocatalysis

      Visible Light Photocatalysis of [2+2] Styrene Cycloadditions by Energy Transfer (pages 10329–10332)

      Dr. Zhan Lu and Prof. Tehshik P. Yoon

      Article first published online: 10 SEP 2012 | DOI: 10.1002/anie.201204835

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      Hip to be square: Styrenes participate in [2+2] cycloadditions upon irradiation with visible light in the presence of an iridium(III) polypyridyl complex. In contrast to previous reports of visible light photoredox catalysis, the mechanism of this process involves photosensitization by energy transfer and not electron transfer.

    18. Oligoacenes

      Intermolecular Oxidative Annulation of 2-Aminoanthracenes to Diazaacenes and Aza[7]helicenes (pages 10333–10336)

      Kiyohiko Goto, Ryuichi Yamaguchi, Dr. Satoru Hiroto, Hiroshi Ueno, Prof. Dr. Tsuyoshi Kawai and Prof. Dr. Hiroshi Shinokubo

      Article first published online: 10 SEP 2012 | DOI: 10.1002/anie.201204863

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      Which way to go: The product distribution in the efficient oxidation of 2-aminoanthracene derivatives to pyrazine- and pyrrole-fused bisanthracenes can be controlled by additives (see scheme; TFA=trifluoroacetic acid, DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone). The pyrrole-fused dimer can be regarded as an aza[7]helicene with a stable helical conformation.

    19. Asymmetric Synthesis

      Enantioselective Aza-Morita–Baylis–Hillman Reactions of Acrylonitrile Catalyzed by Palladium(II) Pincer Complexes having C2-Symmetric Chiral Bis(imidazoline) Ligands (pages 10337–10341)

      Kengo Hyodo, Prof. Shuichi Nakamura and Prof. Norio Shibata

      Article first published online: 17 SEP 2012 | DOI: 10.1002/anie.201204891

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      Simple and efficient: The first highly enantioselective aza-Morita–Baylis–Hillman reaction between acrylonitrile and imines has been developed. Excellent yields and enantioselectivities were observed for the reaction of various imines using chiral phebim/PdII complexes (1; see scheme). This process offers a simple and efficient route for the synthesis of functionalized α-methylene-β-aminonitriles and their derivatives.

    20. Aromaticity

      Reactions of Metal–Metal Quintuple Bonds with Alkynes: [2+2+2] and [2+2] Cycloadditions (pages 10342–10346)

      Dr. Hong-Zhang Chen, Shih-Cheng Liu, Chun-Hsu Yen, Prof. Dr. Jen-Shiang K. Yu, Yun-Jen Shieh, Ting-Shen Kuo and Prof. Dr. Yi-Chou Tsai

      Article first published online: 14 SEP 2012 | DOI: 10.1002/anie.201205027

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      High five! The quintuply bonded molybdenum amidinate 1 reacts with two equivalents of 1-pentyne through a [2+2+2] cycloaddition reaction to give the first examples of the benzannulated product 2. The C4Mo2 rings exhibit aromatic character. Treatment of 1 with internal alkynes afforded the 2:1 and 1:1 [2+2] cycloadducts, which are mechanistically associated with the formation of 2.

    21. Total Synthesis

      Convergent Chemical Synthesis of Proteins by Ligation of Peptide Hydrazides (pages 10347–10350)

      Dr. Ge-Min Fang, Jia-Xing Wang and Prof. Dr. Lei Liu

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201203843

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      Coming together: A generally applicable strategy for convergent chemical synthesis of proteins from multiple peptide segments is developed on the basis of the ligation of peptide hydrazides. The peptide hydrazide intermediates can be made at low cost and the new strategy is used in the synthesis of the 142 residue model protein RpS25 from six peptide segments. PG=protecting group.

    22. Solar Cells

      A Selenium-Based Cathode for a High-Voltage Tandem Photoelectrochemical Solar Cell (pages 10351–10354)

      Jin Qian, Prof. Ke-Jian Jiang, Dr. Jin-Hua Huang, Dr. Qi-Sheng Liu, Prof. Lian-Ming Yang and Prof. Yanlin Song

      Article first published online: 10 SEP 2012 | DOI: 10.1002/anie.201204108

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      High voltage: A selenium-based photocathode has been developed for a photoelectrochemical solar cell with a high open-circuit voltage Voc of 318 mV and an efficiency of 0.34 %. A higher Voc of 940 mV was realized in a tandem solar cell with a conventional N719 dye-sensitized photoanode, giving an efficiency of 0.98 %.

    23. Chirality

      Planar-Chiral [7]Orthocyclophanes (pages 10355–10358)

      Prof. Dr. Katsuhiko Tomooka, Chisato Iso, Dr. Kazuhiro Uehara, Dr. Masaki Suzuki, Rie Nishikawa-Shimono and Dr. Kazunobu Igawa

      Article first published online: 13 SEP 2012 | DOI: 10.1002/anie.201204484

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      Just plain chiral: The [7]orthocyclophanes 1, having an E-olefinic ansa chain, exhibit planar chirality at ambient temperature and their stereochemical stabilities are highly dependent upon the embedded X group in the ansa chain. Inter- and intramolecular transformations of 1 (where X=NTs) provide a variety of nitrogen-containing chiral molecules in a stereospecific manner. Ts=4-toluenesulfonyl.

    24. Asymmetric Fluorination

      Enantioselective Synthesis of β,γ-Unsaturated α-Fluoroesters Catalyzed by N-Heterocyclic Carbenes (pages 10359–10363)

      Dr. Yu-Ming Zhao, Man Sing Cheung, Prof. Dr. Zhenyang Lin and Prof. Dr. Jianwei Sun

      Article first published online: 10 SEP 2012 | DOI: 10.1002/anie.201204521

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      NHC meets F: NHC-bound enolates undergo a catalytic asymmetric fluorination reaction to β,γ-unsaturated α-fluoroesters, which are obtained with good efficiency and stereoselectivity (see scheme, NFSI=N-fluorobenzenesulfonimide). The strategy overcomes possible challenges, such as fluorination in the γ position and difluorination. Experimental evidence combined with DFT calculations provides insight into the reaction mechanism.

    25. Synthetic Method

      Catalyst-Controlled Chemoselective Arylation of 2-Aminobenzimidazoles (pages 10364–10367)

      Dr. Satoshi Ueda and Prof. Dr. Stephen L. Buchwald

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201204710

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      What N would you like? The chemoselective and complementary Pd- and Cu-catalyzed N-arylation of 2-aminobenzimidazoles is described. Selective N-arylation of the amino group was achieved with a Pd-catalyzed method, while selective N-arylation of azole nitrogen was achieved with a Cu-catalyzed procedure (see scheme).

    26. Confined Nanocatalysts

      A Template Carbonization Strategy to Synthesize Ordered Mesoporous Silica Microspheres with Trapped Sulfonated Carbon Nanoparticles for Efficient Catalysis (pages 10368–10372)

      Qin Yue, Minghong Wang, Jing Wei, Prof. Dr. Yonghui Deng, Tianyi Liu, Prof. Dr. Renchao Che, Prof. Dr. Bo Tu and Prof. Dr. Dongyuan Zhao

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201204719

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      A facile template carbonization strategy has been used for the synthesis of ordered mesoporous silica microspheres with sulfonated carbon nanoparticles trapped inside by combining solvent-evaporation-induced aggregating assembly, in situ carbonization, and sulfonation treatments. The obtained SO3H-bearing microspheres show an excellent catalytic performance in the condensation reaction of benzaldehyde with ethylene glycol.

    27. Metal–Organic Frameworks

      Automated Diffraction Tomography for the Structure Elucidation of Twinned, Sub-micrometer Crystals of a Highly Porous, Catalytically Active Bismuth Metal–Organic Framework (pages 10373–10376)

      Mark Feyand, Dr. Enrico Mugnaioli, Frederik Vermoortele, Bart Bueken, Dr. Johannes M. Dieterich, Tim Reimer, Dr. Ute Kolb, Prof. Dr. Dirk de Vos and Prof. Dr. Norbert Stock

      Article first published online: 13 SEP 2012 | DOI: 10.1002/anie.201204963

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      A combined approach: A permanent highly porous bismuth-containing metal–organic framework (CAU-7) has been synthesized and its structure determined by a combination of electron diffraction, Rietveld refinement, and DFT calculations. The compound is catalytically active in the hydroxymethylation of furan (see picture).

    28. Gold Catalysis

      Gold-Catalyzed Functionalization of Unactivated C(sp3)[BOND]H Bonds by Hydride Transfer Facilitated by Alkynylspirocyclopropanes (pages 10377–10381)

      Prof. Dr. José Barluenga, Dr. Rita Sigüeiro, Dr. Rubén Vicente, Prof. Dr. Alfredo Ballesteros, Prof. Dr. Miguel Tomás and Prof. Dr. Miguel A. Rodríguez

      Article first published online: 13 SEP 2012 | DOI: 10.1002/anie.201205051

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      A Golden Gate: Alkynylspirocyclopropanes served as a template for the development of gold-catalyzed hydride transfer from unactivated C(sp3)[BOND]H bonds to electronically neutral alkynes. A variety of interesting carbocyclic structures can be accessed selectively with the appropriate choice of the reaction conditions. Mechanistic studies support a sequential gold-catalyzed cleavage of C[BOND]H and C[BOND]C bonds.

    29. Organometallic Chemistry

      Electrophilic Trifluoromethanesulfanylation of Organometallic Species with Trifluoromethanesulfanamides (pages 10382–10385)

      François Baert, Julie Colomb and Dr. Thierry Billard

      Article first published online: 13 SEP 2012 | DOI: 10.1002/anie.201205156

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      It's so easy! Direct trifluoromethanesulfanylation reactions remain difficult to perform because of the lack of reagents that are stable and easy to handle. Trifluoromethanesulfanamides are reagents which, in combination with readily available Grignard reagents, can be used by those without experience in fluorine chemistry to easily synthesize trifluoromethylthioethers.

    30. Analytical Methods

      Observation of Subcellular Metabolite Gradients in Single Cells by Laser Ablation Electrospray Ionization Mass Spectrometry (pages 10386–10389)

      Jessica A. Stolee, Dr. Bindesh Shrestha, Getachew Mengistu and Prof. Akos Vertes

      Article first published online: 5 SEP 2012 | DOI: 10.1002/anie.201205436

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      Getting to the point: Cell microdissection and analysis by the title technique was used to study the compartmentalization of metabolites within subcellular domains. Experiments performed on plant epidermal cells imply that there are significant differences between the metabolite composition in the nucleus and the cytoplasm. This technique is applicable to other cell types and may give insight into the mechanisms of disease and drug delivery.

    31. Heterocycles

      Gallium(III)-Catalyzed Three-Component (4+3) Cycloaddition Reactions (pages 10390–10393)

      Xinping Han, Hui Li, Prof. Dr. Russell P. Hughes and Prof. Dr. Jimmy Wu

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201205238

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      Direct approach to indoles: The title reaction generates cyclohepta[b]indole derivatives in a single step at room temperature (see scheme). Exclusion of air or moisture is not required. DFT calculations support a stepwise cyclization event, and the versatility of the method is demonstrated by providing quick access to a library of cyclohepta[b]indole analogues.

    32. Biosensors

      Continuous Evolution Profiles for Electronic-Tongue-Based Analysis (pages 10394–10398)

      Dr. Yanxia Hou, Maria Genua, Dr. Dayane Tada Batista, Dr. Roberto Calemczuk, Dr. Arnaud Buhot, Pauline Fornarelli, Dr. Jamal Koubachi, Prof. David Bonnaffé, Els Saesen, Dr. Cédric Laguri, Dr. Hugues Lortat-Jacob and Dr. Thierry Livache

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201205346

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      Licking the problem: A new type of electronic tongue was constructed by self-assembly on the surface of a surface plasmon resonance (SPR) imaging prism with combinations of simple building blocks. The resulting combinatorial array was used to detect proteins in solution (see scheme) by using SPR imaging to monitor the interactions. The signal from each spot was dependent on its composition and the protein infused, and correlated with the response of its neighbors.

    33. C[BOND]H Activation

      Synthesis of Hexahydroindoles by Intramolecular Cmath image[BOND]H Alkenylation: Application to the Synthesis of the Core of Aeruginosins (pages 10399–10402)

      Dr. Julien Sofack-Kreutzer, Dr. Nicolas Martin, Dr. Alice Renaudat, Dr. Rodolphe Jazzar and Prof. Dr. Olivier Baudoin

      Article first published online: 10 SEP 2012 | DOI: 10.1002/anie.201205403

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      Give me five: Pd-catalyzed intramolecular Cmath image[BOND]H arylations have been successfully extended to alkenylations. This method shows remarkable selectivity and gives synthetically useful hexahydroindoles, as illustrated with the synthesis of the octahydroindole core of the aeruginosin family of natural products (see picture).

    34. Proximal Side Control

      Experimental Documentation of the Structural Consequences of Hydrogen-Bonding Interactions to the Proximal Cysteine of a Cytochrome P450 (pages 10403–10407)

      Dr. Piotr J. Mak, Dr. Yuting Yang, Dr. Sangchoul Im, Prof. Lucy A. Waskell and Prof. James R. Kincaid

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201205912

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      Reactivity control: Resonance Raman spectroscopy is used to document, for the first time, a 6 cm−1 decrease of the Fe[BOND]S stretch by introducing an H-bond donor into the proximal pocket of a cytochrome P450, which interacts with the cysteine thiolate axial ligand (see picture). The anticipated trans-effect on bound exogenous ligands is also confirmed.

    35. Organocatalysis

      Structures and Reactivities of O-Methylated Breslow Intermediates (pages 10408–10412)

      M. Sc. Biplab Maji and Prof. Dr. Herbert Mayr

      Article first published online: 11 SEP 2012 | DOI: 10.1002/anie.201204524

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      As close as you can get: Since Breslow intermediates usually exist in their keto form, their O-protected tautomers may be considered as their closest isolable relatives. A series of these compounds have been synthesized, their structures determined, and the kinetics of their reactions with electrophiles investigated.

    36. Self-Assembled Monolayers

      Parallel Imaging and Template-Free Patterning of Self-Assembled Monolayers with Soft Linear Microelectrode Arrays (pages 10413–10416)

      Andreas Lesch, Britta Vaske, Frank Meiners, Dmitry Momotenko, Dr. Fernando Cortés-Salazar, Prof. Dr. Hubert H. Girault and Prof. Dr. Gunther Wittstock

      Article first published online: 17 SEP 2012 | DOI: 10.1002/anie.201205347

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      Reagents were generated locally on an array of eight individually addressable electrodes in order to modify self-assembled monolayers. Since the array was manufactured in a soft polymer material, it can have mechanical contact with a delicate sample without inducing defects. Lengthy leveling procedures are not necessary and the scan times can be shortened.

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