Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 24

June 10, 2013

Volume 52, Issue 24

Pages 6113–6338

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    1. You have free access to this content
      Cover Picture: Regioselectively Functionalized Pyridines from Sustainable Resources (Angew. Chem. Int. Ed. 24/2013) (page 6113)

      Stefan Michlik and Prof. Dr. Rhett Kempe

      Article first published online: 4 JUN 2013 | DOI: 10.1002/anie.201303642

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      In the sustainable Ir-catalyzed synthesis of pyridine derivatives described by R. Kempe and S. Michlik in their Communication on page 6326 ff., alcohols and 1,3-amino alcohols are deoxygenated and selectively linked in C[BOND]N and C[BOND]C bond-forming steps. Three equivalents of hydrogen gas are liberated per generated pyridine unit (see reaction scheme). The wood and blossums in the background underline the fact that the starting materials can be obtained from renewable resources.

    2. You have free access to this content
      Inside Cover: Rational Design of an Apoptosis-Inducing Photoreactive DNA Intercalator (Angew. Chem. Int. Ed. 24/2013) (page 6114)

      Nico Ueberschaar, Dr. Hans-Martin Dahse, Tom Bretschneider and Prof. Dr. Christian Hertweck

      Article first published online: 28 MAY 2013 | DOI: 10.1002/anie.201303645

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      Vinylchartreusin , a chartreusin analogue that intercalates in double-stranded DNA, was prepared by mutasynthesis to design a photoactivatable antitumoral agent that is able to form [2+2] photoadducts. In their Communication on page 6185 ff., C. Hertweck and co-workers report substantially higher antiproliferative activities of this compound compared with the natural product upon irradiation with visible light. Colorectal cancer cells (see background) show signs of apoptosis after treatment with vinylchartreusin and blue light.

    3. You have free access to this content
      Inside Back Cover: Azacalixphyrin: The Hidden Porphyrin Cousin Brought to Light (Angew. Chem. Int. Ed. 24/2013) (page 6339)

      Zhongrui Chen, Dr. Michel Giorgi, Prof. Denis Jacquemin, Dr. Mourad Elhabiri and Dr. Olivier Siri

      Article first published online: 31 MAY 2013 | DOI: 10.1002/anie.201303670

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      A porphyrin aza analogue that contains no pyrrol subunits absorbs in the entire visible region. D. Jacquemin, O. Siri, and co-workers show in their Communication on page 6250 ff. that the central 16-membered ring containing four nitrogen atoms has 18 delocalized π electrons, and is thus aromatic. This compound is analogous to both azacalix[4]arenes and porphyrins, which is reflected in the name of this new family of macrocycles, azacalixphyrins.

    4. You have free access to this content
      Back Cover: The Fatty Acid Composition of Diacylglycerols Determines Local Signaling Patterns (Angew. Chem. Int. Ed. 24/2013) (page 6340)

      Dr. André Nadler, Dr. Gregor Reither, Suihan Feng, Frank Stein, Dr. Sabine Reither, Dr. Rainer Müller and Priv.-Doz. Dr. Carsten Schultz

      Article first published online: 31 MAY 2013 | DOI: 10.1002/anie.201304203

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      Photoactivatable or “caged” derivatives of signaling molecules are important tools for manipulating intracellular events with spatial and temporal resolution. In their Communication on page 6330 ff., C. Schultz and co-workers demonstrate that regionally limited photoactivation simultaneously leads to a local protein kinase C and a global calcium response. Surprisingly, the orchestration of these effects seems to depend on the fatty acid composition of the released lipid.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 24/2013 (pages 6117–6129)

      Article first published online: 5 JUN 2013 | DOI: 10.1002/anie.201390024

  3. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    1. Peter J. Sadler (page 6136)

      Article first published online: 20 FEB 2013 | DOI: 10.1002/anie.201209484

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      “My biggest motivation is the excitement of discovery. My favorite piece of research is a discovery that you had not intended to make in the first place …” This and more about Peter J. Sadler can be found on page 6136.

  5. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Book Review
    8. Highlights
    9. Essay
    10. Review
    11. Communications
    1. Introduction to Bioorganic Chemistry and Chemical Biology. By David Van Vranken and Gregory A. Weiss. (page 6138)

      Katja Schmitz

      Article first published online: 16 MAY 2013 | DOI: 10.1002/anie.201303373

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      Garland Science (Taylor & Francis), 2012. 504 pp., softcover, £ 48.00.—ISBN 978-0815342144

  7. Highlights

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

      A Supramolecular Peptide Synthesizer (pages 6140–6142)

      M. Sc. Jordi Bertran-Vicente and Prof. Dr. Christian P. R. Hackenberger

      Article first published online: 17 MAY 2013 | DOI: 10.1002/anie.201301825

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      Line up for synthesis! In a recent report the Leigh group described a rotaxane-based setup for the sequence-specific synthesis of small peptides, which runs automatically once started. This molecular machine combines elements from both chemical and biochemical peptide (bio-)syntheses, which are discussed in this Highlight.

    2. Hydrogenase Mimics

      Catalytic Hydrogen Oxidation: Dawn of a New Iron Age (pages 6143–6145)

      Dr. Trevor R. Simmons and Dr. Vincent Artero

      Article first published online: 21 MAY 2013 | DOI: 10.1002/anie.201302908

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      One metal or two? Recent results in the design of hydrogenase mimics have resulted in NiFe- and Fe-based complexes (see picture) that split molecular H2 into electrons and protons. Although these compounds are still far from technological application they improve our understanding of how nature exploits abundant metals to achieve complex reactions.

  8. Essay

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

      Alfred Werner: A Forerunner to Modern Inorganic Chemistry (pages 6146–6153)

      Prof. em. Dr. Helmut Werner

      Article first published online: 13 MAY 2013 | DOI: 10.1002/anie.201208389

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      Numerous honors were bestowed on Alfred Werner, who in 1913 was the first Swiss scientist to be awarded the Nobel Prize in Chemistry. This Essay gives an overview of Werner′s scientific work and its significance beyond coordination chemistry. Picture: gray Co, red O, blue N, yellow H.

  9. Review

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

      Emerging Strategies for the Total Synthesis of Inorganic Nanostructures (pages 6154–6178)

      Matthew R. Buck and Prof. Raymond E. Schaak

      Article first published online: 22 APR 2013 | DOI: 10.1002/anie.201207240

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      Nanoscale total synthesis: Diverse nanoparticle reaction libraries can be applied sequentially and predictably to construct complex multicomponent nanoscale architectures, in analogy to the total synthesis concept used to construct large and complex molecules.

  10. Communications

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

      A Thermoresponsive Hydrogel Formed from a Star–Star Supramolecular Architecture (pages 6180–6184)

      Dr. Zhong-Xing Zhang, Dr. Kerh Li Liu and Prof. Dr. Jun Li

      Article first published online: 10 MAY 2013 | DOI: 10.1002/anie.201301956

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      Smart stars: A novel star–star supramolecular architecture was self-assembled from a star-shaped adamantyl-terminated 8-arm poly(ethylene glycol) and a star-shaped poly(N-isopropylacrylamide) with a β-cyclodextrin core through inclusion complexation. The star–star supramolecules further self-aggregated into a 3D network in response to temperature change, forming a thermoresponsive reversible “smart” hydrogel.

    2. Antitumor Agents

      Rational Design of an Apoptosis-Inducing Photoreactive DNA Intercalator (pages 6185–6189)

      Nico Ueberschaar, Dr. Hans-Martin Dahse, Tom Bretschneider and Prof. Dr. Christian Hertweck

      Article first published online: 6 MAY 2013 | DOI: 10.1002/anie.201302439

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      Light on DNA intercalators: Molecular modeling and mutasynthesis were employed to rationally tailor the antitumoral agent chartreusin into a vinyl-substituted derivative. Exposure with visible light dramatically improved antiproliferative activities owing to covalent binding with DNA and induction of apoptosis. The results hold promise for a more efficient chemotherapy, in particular for selectively treating tumors with light probes.

    3. Nanoparticles for Stem Cells

      Multimodal Magnetic Core–Shell Nanoparticles for Effective Stem-Cell Differentiation and Imaging (pages 6190–6195)

      Birju Shah, Perry T. Yin, Shraboni Ghoshal and Prof. Ki-Bum Lee

      Article first published online: 6 MAY 2013 | DOI: 10.1002/anie.201302245

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      Special delivery! The title system, composed of a highly magnetic core surrounded by a thin uniform gold shell, has been synthesized and applied to the magnetically facilitated delivery of genetic material (siRNA or plasmid DNA) into neural stem cells (NSCs) for controlling their neural differentiation in a spatiotemporally controlled, biocompatible manner.

    4. Asymmetric Heterogeneous Catalysis

      Self-Assembling Neodymium/Sodium Heterobimetallic Asymmetric Catalyst Confined in a Carbon Nanotube Network (pages 6196–6201)

      Takanori Ogawa, Dr. Naoya Kumagai and Prof. Dr. Masakatsu Shibasaki

      Article first published online: 2 MAY 2013 | DOI: 10.1002/anie.201302236

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      Confined cat works better: A self-assembling heterobimetallic catalyst, comprised of a Nd/Na/amide ligand confined in an entangled multiwalled carbon nanotube (MWNT) network, outperforms the unconfined catalyst in anti-selective catalytic asymmetric nitroaldol reactions. The confined catalyst could be used repeatedly through simple filtration, and was applied to a concise enantioselective synthesis of anacetrapib.

    5. Single-Molecule Conductance

      Highly Conductive [3×n] Gold-Ion Clusters Enclosed within Self-Assembled Cages (pages 6202–6205)

      Dr. Manabu Kiguchi, Junichi Inatomi, Yuuta Takahashi, Ryota Tanaka, Takafumi Osuga, Dr. Takashi Murase, Prof. Dr. Makoto Fujita, Dr. Tomofumi Tada and Prof. Dr. Satoshi Watanabe

      Article first published online: 29 APR 2013 | DOI: 10.1002/anie.201301665

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      Ion nanowire: Electron transport through discrete gold-ion arrays within coordination cages was directly measured between Au nanogap electrodes (see picture) using STM. Precise calibration of the electron transport distance demonstrates that Au-ion arrays exhibit good conductance and only moderate loss with increasing transport length.

    6. Analytical Methods

      Two-Color Probe to Monitor a Wide Range of pH Values in Cells (pages 6206–6209)

      Min Hee Lee, Ji Hye Han, Jae Hong Lee, Nayoung Park, Rajesh Kumar, Prof. Chulhun Kang and Prof. Jong Seung Kim

      Article first published online: 22 APR 2013 | DOI: 10.1002/anie.201301894

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      High-tech pH paper: A “chameleon” pH probe composed of rhodamine (red, see scheme) and fluorescein (green) units emits at wavelengths of 580 nm and 512 nm, where the intensities show a contrary response to pH changes. Confocal microscopy of HeLa cells with this probe reveals red and green spots; the ratio of these signals can be calibrated to give the pH value of the respective organelle.

    7. Protein Semi-Synthesis

      Expressed Protein Ligation at Methionine: N-Terminal Attachment of Homocysteine, Ligation, and Masking (pages 6210–6213)

      Dr. Tomohiro Tanaka, Anne M. Wagner, John B. Warner, Yanxin J. Wang and Prof. E. James Petersson

      Article first published online: 29 APR 2013 | DOI: 10.1002/anie.201302065

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      A useful handle: One major limitation of protein semi-synthesis is the need for Cys at the ligation site in native chemical ligation reactions. It is shown that a transferase enzyme can deliver homocysteine to the N-terminus of an expressed protein (see scheme). Homocysteine can be used in a ligation reaction and then converted to Met. This allows one to use the MetArg or MetLys motif as a point of disconnection in semi-synthesis.

    8. IR Spectroscopy

      Ultrafast Hopping from Band to Band: Assigning Infrared Spectra based on Vibrational Energy Transfer (pages 6214–6217)

      Henrike M. Müller-Werkmeister, Dr. Yun-Liang Li, Dr. Eliza-Beth W. Lerch, Dr. Damien Bigourd and Prof. Dr. Jens Bredenbeck

      Article first published online: 29 APR 2013 | DOI: 10.1002/anie.201209916

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      Distance matters: Interpretation of infrared spectra regularly involves the assignment of absorption bands to certain functional groups of the molecule. Distance-dependent vibrational energy transfer can be used for exact band assignment in molecules in which assignment is difficult and quantum chemical computations are contradictory.

    9. siRNA Conjugates

      Acidic pH-Responsive siRNA Conjugate for Reversible Carrier Stability and Accelerated Endosomal Escape with Reduced IFNα-Associated Immune Response (pages 6218–6221)

      Hiroyasu Takemoto, Dr. Kanjiro Miyata, Shota Hattori, Dr. Takehiko Ishii, Tomoya Suma, Satoshi Uchida, Dr. Nobuhiro Nishiyama and Dr. Kazunori Kataoka

      Article first published online: 29 APR 2013 | DOI: 10.1002/anie.201300178

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      An siRNA conjugate is based on an acid-labile maleic acid amide linkage for programmed transfer of siRNA from the endosome to the cytosol and siRNA release in the cell interior. The procedure relies on reversible stability in response to endosomal acidic pH value. The complexed polyionic conjugate achieved gene silencing in cultured cancerous cells with negligible side effects.

    10. Self-Assembled Monolayers

      Self-Assembled Monolayers of Phosphonic Acids with Enhanced Surface Energy for High-Performance Solution-Processed N-Channel Organic Thin-Film Transistors (pages 6222–6227)

      Danqing Liu, Xiaomin Xu, Yaorong Su, Zikai He, Prof. Jianbin Xu and Prof. Qian Miao

      Article first published online: 3 MAY 2013 | DOI: 10.1002/anie.201300353

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      Add an O: A new strategy for preparing solution-processed organic thin-film transistors (OTFTs) is based on enhancing the surface energy of self-assembled monolayers (SAMs) by inserting polar oxygen atoms into the long alkyl chain of phosphonic acids. SAMs of these phosphonic acids on a high-k metal oxide layer lead to solution-processed n-channel OTFTs with average field effect mobilities of up to 2.5 cm2 V−1 s−1 and low operational voltages.

    11. Porous Organic Materials

      Tandem Synthesis of Photoactive Benzodifuran Moieties in the Formation of Microporous Organic Networks (pages 6228–6232)

      Narae Kang, Dr. Ji Hoon Park, Kyoung Chul Ko, Jiseul Chun, Eunchul Kim, Dr. Hee-Won Shin, Dr. Sang Moon Lee, Dr. Hae Jin Kim, Prof. Tae Kyu Ahn, Prof. Jin Yong Lee and Prof. Seung Uk Son

      Article first published online: 29 APR 2013 | DOI: 10.1002/anie.201300655

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      Tiny pores: Benzodifuran moieties were introduced into microporous organic networks (MONs) through a tandem process consisting of Sonogashira coupling of 1,3,5-triethynylbenzene and 2,5-diiodo-1,4-hydroquinone and intramolecular cyclization. The resultant benzodifuran-containing MON showed promising photocatalytic activities in the oxidative conversion of primary amines into imines.

    12. Stimuli-Responsive Gels

      γ-Ray-Responsive Supramolecular Hydrogel Based on a Diselenide-Containing Polymer and a Peptide (pages 6233–6237)

      Wei Cao, Xiaoli Zhang, Xiaoming Miao, Prof. Zhimou Yang and Prof. Huaping Xu

      Article first published online: 29 APR 2013 | DOI: 10.1002/anie.201300662

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      An overwhelming response: The exposure of a supramolecular hydrogel based on a diselenide-containing polymer and a peptide amphiphile containing a drug moiety to γ radiation led to a gel–sol transition owing to the oxidative cleavage of diselenide bonds in the polymer main chain (see picture). The hydrogel can also act as a UV-mediated drug self-delivery system and suggests a new avenue for combined radio- and chemotherapy.

    13. Electrochemistry

      In situ Seamless Magnetic Measurements for Solid-State Electrochemical Processes in Prussian Blue Analogues (pages 6238–6241)

      Dr. Tetsuya Yamada, Kantaro Morita, Dr. Heng Wang, Keita Kume, Dr. Hirofumi Yoshikawa and Prof. Kunio Awaga

      Article first published online: 25 APR 2013 | DOI: 10.1002/anie.201301084

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      Seamless observation: Magnetic measurements in a solid-state electrochemical environment have been developed and applied to a mixed-valent chromium Prussian blue analogue (PBA) ferrimagnet. Battery cells containing PBA as a cathode active material were inserted into a SQUID and the PBA reduction during battery discharge was controlled. Magnetic changes were revealed that can be understood by the redox-induced spin changes of the Cr ions.

    14. Elemental Photocatalysts

      Visible-Light-Responsive β-Rhombohedral Boron Photocatalysts (pages 6242–6245)

      Dr. Gang Liu, Dr. Li-Chang Yin, Ping Niu, Wei Jiao and Prof. Hui-Ming Cheng

      Article first published online: 29 APR 2013 | DOI: 10.1002/anie.201302238

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      It's elemental! β-Rhombohedral boron was investigated as an elemental photocatalyst. Boron crystals were found to be photocatalytically active in the generation of .OH radicals under irradiation with visible light (see picture); however, the presence of an amorphous oxide layer on the surface of the crystals impaired their photocatalytic activity.

    15. Protein Design

      A Single Mutation in a Regulatory Protein Produces Evolvable Allosterically Regulated Catalyst of Nonnatural Reaction (pages 6246–6249)

      Dr. Olesia V. Moroz, Dr. Yurii S. Moroz, Dr. Yibing Wu, Alissa B. Olsen, Dr. Hong Cheng, Korrie L. Mack, Jaclyn M. McLaughlin, Elizabeth A. Raymond, Krystyna Zhezherya, Prof. Dr. Heinrich Roder and Prof. Dr. Ivan V. Korendovych

      Article first published online: 29 APR 2013 | DOI: 10.1002/anie.201302339

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      It only takes one mutation: A strategically placed single mutation in a non-enzymatic protein scaffold produced AlleyCat, a small, allosterically regulated catalyst of Kemp elimination. In only seven rounds of directed evolution the enzymatic efficiency of the original 74 amino acid residue catalyst was improved more than 220-fold to achieve a kcat value higher than that of catalytic antibodies for the same reaction, still preserving allosteric regulation.

    16. Porphyrin Analogues

      Azacalixphyrin: The Hidden Porphyrin Cousin Brought to Light (pages 6250–6254)

      Zhongrui Chen, Dr. Michel Giorgi, Prof. Denis Jacquemin, Dr. Mourad Elhabiri and Dr. Olivier Siri

      Article first published online: 29 MAY 2013 | DOI: 10.1002/anie.201301217

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      No pyrrol: Azacalixphyrin (see picture), a novel isostructural and isoelectronic “pyrrol-free” analogue of porphyrins is easily prepared in two straightforward steps. The azacalixphyrin is aromatic, absorbs in the entire visible region, and is highly stable (even in the presence of water under air) owing to its unusual bis-zwitterionic character.

    17. Synthetic Methods

      Silver-Mediated Cycloaddition of Alkynes with CF3CHN2: Highly Regioselective Synthesis of 3-Trifluoromethylpyrazoles (pages 6255–6258)

      Feng Li, Jing Nie, Long Sun, Yan Zheng and Prof. Jun-An Ma

      Article first published online: 24 APR 2013 | DOI: 10.1002/anie.201301870

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      Silver screen: The title reaction provides a convenient and efficient method for the construction of 5-substituted 3-trifluoromethylpyrazoles under mild reaction conditions. By using this protocol, the marketed drug Celecoxib (antiarthritic) could be easily synthesized (see scheme; DMF=N,N-dimethylformamide).

    18. Cycloaddition

      Direct Observation of a Cationic Gold(I)–Bicyclo[3.2.0]hept-1(7)-ene Complex Generated in the Cycloisomerization of a 7-Phenyl-1,6-enyne (pages 6259–6261)

      Rachel E. M. Brooner, Timothy J. Brown and Prof. Ross A. Widenhoefer

      Article first published online: 25 APR 2013 | DOI: 10.1002/anie.201301640

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      The reaction of enyne 1 with a 1:1 mixture of [LAuCl] and AgSbF6 in CD2Cl2 at −20 °C gave the gold complex 2 in 97 % yield (NMR spectroscopy). Warming a solution of 2 at 25 °C led to 1,3-H migration (t1/2≈16 min) to form the gold complex 3 with 96 % selectivity. 13C NMR analysis of 2 and 3 showed predominant metallacyclopropane character of the gold[BOND]bicyclo[3.2.0]heptene bond.

    19. Asymmetric Catalysis

      Enantioselective Construction of Highly Substituted Vinylidenecylopentanes by Palladium-Catalyzed Asymmetric [3+2] Cycloaddition Reaction (pages 6262–6264)

      Prof. Barry M. Trost and Autumn Maruniak

      Article first published online: 25 APR 2013 | DOI: 10.1002/anie.201300275

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      A new cycloadduct: The title reaction of methylene-trimethylenemethane (TMM) with α,β-unsaturated N-acyl pyrroles is an efficient method for the construction of vinylidenecyclopentanes. An asymmetric protocol using this unique donor forms cycloadducts in excellent yield and enantioselectivity, making use of a bisdiamidophosphite ligand derived from trans-1,2-stilbenediamine.

    20. Ethylene Oxidation

      Low-Temperature Oxidation of Ethylene over Platinum Nanoparticles Supported on Mesoporous Silica (pages 6265–6268)

      M. Sc. Chuanxia Jiang, Dr. Kenji Hara and Prof. Dr. Atsushi Fukuoka

      Article first published online: 3 MAY 2013 | DOI: 10.1002/anie.201300496

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      Fresh fruit not rotting vegetables: Ethylene released from fruits and vegetables accelerates their spoiling even in refrigerators. To oxidatively remove traces of ethylene from a gas mix, supported metal nanoparticles were tested. A Pt catalyst supported on mesoporous silica gave complete conversion of 50 ppm ethylene even at 0 °C. IR experiments suggest the facile oxidation of CO over Pt on the silica supports is the key to the catalytic activity.

    21. Cleaving Amines by Water

      Direct Deamination of Primary Amines by Water To Produce Alcohols (pages 6269–6272)

      Dr. Julia R. Khusnutdinova, Yehoshoa Ben-David and Prof. David Milstein

      Article first published online: 25 APR 2013 | DOI: 10.1002/anie.201301000

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      Just add water! The title reaction is catalyzed by an acridine-based pincer complex (1, see scheme). This one-step transformation uses water as the only reagent in the absence of additional bases, oxidants, or reductants. Cyclization of 1,4-diaminobutane and 1,6-diaminohexane catalyzed by 1 leads to the formation of pyrrolidine and azepane, respectively.

    22. Synthetic Methods

      You have full text access to this OnlineOpen article
      Iridium-Catalyzed 1,3-Hydrogen Shift/Chlorination of Allylic Alcohols (pages 6273–6276)

      Dr. Nanna Ahlsten, Dr. Antonio Bermejo Gómez and Prof. Dr. Belén Martín-Matute

      Article first published online: 24 APR 2013 | DOI: 10.1002/anie.201301013

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      Tandem: Allylic alcohols react with N-chlorosuccinimide (NCS) in a tandem 1,3-H shift/C[BOND]Cl bond formation leading to α-chloroketones and α-chloroaldehydes. The reactions proceed with complete selectivity to give single constitutional isomers of monochlorinated carbonyl compounds. The utility of the transformation is illustrated by the straightforward synthesis of 4,5-disubstituted 2-aminothiazoles from allylic alcohols.

    23. Homogeneous Catalysis

      Biarylphosphonite Gold(I) Complexes as Superior Catalysts for Oxidative Cyclization of Propynyl Arenes into Indan-2-ones (pages 6277–6282)

      Guilhem Henrion, Thomas E. J. Chavas, Dr. Xavier Le Goff and Dr. Fabien Gagosz

      Article first published online: 6 MAY 2013 | DOI: 10.1002/anie.201301015

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      Striking gold: A series of variously functionalized propynyl arenes was smoothly converted into indan-2-ones by a new gold(I)-catalyzed oxidative cyclization process. [LAu]NTf2 (Tf=trifluoromethanesulfonyl) is a superior catalyst both in terms of yield and kinetics for the present transformation.

    24. Synthetic Methods

      You have full text access to this OnlineOpen article
      Control of Selectivity in Palladium-Catalyzed Oxidative Carbocyclization/Borylation of Allenynes (pages 6283–6287)

      Dr. Youqian Deng, Teresa Bartholomeyzik and Prof. Dr. Jan-E. Bäckvall

      Article first published online: 17 MAY 2013 | DOI: 10.1002/anie.201301167

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      In control: A highly selective carbocyclization/borylation of allenynes with bis(pinacolato)diboron (B2pin2) under palladium catalysis and with p-benzoquinone (BQ) as the oxidant was developed. The use of either LiOAc⋅2 H2O with 1,2-dichloroethane (DCE) as the solvent or BF3⋅Et2O together with THF is crucial for the selective formation of borylated trienes and vinylallenes, respectively.

    25. Organocatalysis

      Construction of Enantiomerically Enriched Diazo Compounds Using Diazo Esters as Nucleophiles: Chiral Lewis Base Catalysis (pages 6288–6292)

      Haibin Mao, Aijun Lin, Yan Shi, Zhijie Mao, Xuebin Zhu, Weipeng Li, Prof. Dr. Hongwen Hu, Prof. Dr. Yixiang Cheng and Prof. Dr. Chengjian Zhu

      Article first published online: 29 APR 2013 | DOI: 10.1002/anie.201301509

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      Amazing diazo: The title reaction leads to highly functionalized diazo compounds in good yields with excellent enantioselectivities (see scheme; Boc=tert-butoxycarbonyl). The utility of the products was demonstrated by the rapid synthesis of a number of optically pure nitrogen heterocycles. The key to this process was the use of 2,2,2-trifluoroethyl diazoacetate as a superior nucleophilic reagent.

    26. Synthetic Methods

      Ruthenium-Catalyzed Carbonylative C[BOND]C Coupling in Water by Directed C[BOND]H Bond Activation (pages 6293–6297)

      Dr. Anis Tlili, Johannes Schranck, Jola Pospech, Dr. Helfried Neumann and Prof. Dr. Matthias Beller

      Article first published online: 29 APR 2013 | DOI: 10.1002/anie.201301663

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      First things first: The title reaction of arenes bearing ortho-directing groups (DG) in the presence of a ruthenium catalyst and aryl iodide is presented. The reaction is general for variously substituted aryl iodides to give ketones in moderate to good yields, and water serves as the solvent. The system is highly selective towards the mono-carbonylative arylation by ortho C[BOND]H functionalization. cod=cyclo-1,5-octadiene.

    27. Lead Chemistry

      A Base-Stabilized Lead(I) Dimer and an Aromatic Plumbylidenide Anion (pages 6298–6301)

      Siew-Peng Chia, Dr. Hong-Wei Xi, Dr. Yongxin Li, Prof. Dr. Kok Hwa Lim and Dr. Cheuk-Wai So

      Article first published online: 29 APR 2013 | DOI: 10.1002/anie.201301954

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      The aromatic low-valent lead analogue of an indenyl anion (see scheme; 1) undergoes oxidation with SnCl2 to form the base-stabilized lead(I) dimer 2. Reduction of 2 with lithium regenerates 1. These compounds were characterized by NMR spectroscopy and X-ray crystallography.

    28. Nitrous Oxide

      Oxidative Coupling Reactions of Grignard Reagents with Nitrous Oxide (pages 6302–6305)

      Gregor Kiefer, Loïc Jeanbourquin and Prof. Kay Severin

      Article first published online: 13 MAY 2013 | DOI: 10.1002/anie.201302471

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      Catalysis with laughing gas: N2O in combination with transition-metal catalysts allow the oxidative homo- and cross-coupling of Grignard reagents. The reactions can be performed under mild conditions despite the inert character of N2O.

    29. Theoretical Mass Spectrometry

      Towards First Principles Calculation of Electron Impact Mass Spectra of Molecules (pages 6306–6312)

      Prof. Dr. Stefan Grimme

      Article first published online: 29 APR 2013 | DOI: 10.1002/anie.201300158

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      The routine calculation of EI mass spectra is based on a combination of fast quantum chemical methods, molecular dynamics, and the stochastic preparation of “hot” primary ions. All basic elementary processes are considered with minor empiricism and realistic potential free energy surfaces are employed. Reasonable spectra are generated along with detailed information on the corresponding decomposition and reaction mechanisms.

    30. Palladium Complexes

      Palladium-Catalyzed Allylic Substitution at Four-Membered-Ring Systems: Formation of η1-Allyl Complexes and Electrocyclic Ring Opening (pages 6313–6316)

      Dr. Davide Audisio, Dr. Gopinadhanpillai Gopakumar, Dr. Lan-Gui Xie, Dr. Luís G. Alves, Cornelia Wirtz, Prof. Dr. Ana M. Martins, Prof. Dr. Walter Thiel, Dr. Christophe Farès and Dr. Nuno Maulide

      Article first published online: 6 MAY 2013 | DOI: 10.1002/anie.201301034

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      Caught in the act: A series of unique η1-allyl palladium complexes of four-membered cyclic systems bearing β-hydrogens were prepared (see structure). Their unusual structure, reactivity, and unprecedented propensity for undergoing pericyclic reactions were uncovered.

    31. Biomimetic Mineralization

      Heterostructured Calcium Carbonate Microspheres with Calcite Equatorial Loops and Vaterite Spherical Cores (pages 6317–6321)

      Sha-Sha Wang, Andreas Picker, Prof. Dr. Helmut Cölfen and Prof. Dr. An-Wu Xu

      Article first published online: 29 APR 2013 | DOI: 10.1002/anie.201301184

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      It takes two different functional additives to produce the title structures. The proposed mechanism based on the nonclassical particle-mediated crystallization of calcium carbonate demonstrates the individual and cooperative effects of the polymer poly(sodium 4-styrenesulfonate) and small folic acid molecules on the formation of heterostructures at different reaction stages.

    32. Single-Molecule Chemistry

      Distinguishing Alternative Reaction Pathways by Single-Molecule Fluorescence Spectroscopy (pages 6322–6325)

      Arina Rybina, Dr. Carolin Lang, Marcel Wirtz, Kristin Grußmayer, Dr. Anton Kurz, Frank Maier, Dr. Alexander Schmitt, Prof. Oliver Trapp, Prof. Gregor Jung and Dr. Dirk-Peter Herten

      Article first published online: 29 APR 2013 | DOI: 10.1002/anie.201300100

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      Focus on chemical transitions: Epoxidation of a double bond in conjugation to a fluorescent dye was studied at single-molecule level. Direct observation of oxirane formation, indicated as a spectral shift from substrate to product state, revealed an alternative reaction pathway for the epoxidation reaction.

    33. Homogeneous Catalysis

      Regioselectively Functionalized Pyridines from Sustainable Resources (pages 6326–6329)

      Stefan Michlik and Prof. Dr. Rhett Kempe

      Article first published online: 4 JUN 2013 | DOI: 10.1002/anie.201301919

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      Make the most of it! An Ir-catalyzed dehydrogenative condensation of alcohols and 1,3-amino alcohol was used to construct pyridine derivatives regioselectively. This method provides access to unsymmetrically substituted pyridines and tolerates a wide variety of functional groups. Three equivalents of H2 are generated per pyridine unit formed and the alcohol substrates become completely deoxygenated.

    34. Photoactivatable Lipids

      The Fatty Acid Composition of Diacylglycerols Determines Local Signaling Patterns (pages 6330–6334)

      Dr. André Nadler, Dr. Gregor Reither, Suihan Feng, Frank Stein, Dr. Sabine Reither, Dr. Rainer Müller and Priv.-Doz. Dr. Carsten Schultz

      Article first published online: 29 MAY 2013 | DOI: 10.1002/anie.201301716

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      Caged compounds are designed to release biologically active signaling molecules with temporal, spatial, and even subcellular resolution. But how localized does the signal stay? Using the example of diacylglycerol, some signal responses (PKC) are shown to remain spatially distinct while other signals ([Ca2+]i) spread across the entire cell. Surprisingly, this distribution patterns depend on the fatty acid composition of the lipid species.

    35. SECM at Living Cells

      Visualization of Oxygen Consumption of Single Living Cells by Scanning Electrochemical Microscopy: The Influence of the Faradaic Tip Reaction (pages 6335–6338)

      Dr. Michaela Nebel, Stefanie Grützke, Prof. Dr. Nizam Diab, Prof. Dr. Albert Schulte and Prof. Dr. Wolfgang Schuhmann

      Article first published online: 29 APR 2013 | DOI: 10.1002/anie.201301098

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      The influence of the reaction rate at the SECM tip on the overall imaging result is often neglected during respiration studies performed by SECM. The effect of the driving force of the tip reaction is elucidated using a potential pulse profile implemented into a constant-distance mode. Time-dependent data acquisition allows visualization of the transition between a tip behaving as a passive observer and a tip actively inducing transmembrane diffusion of oxygen.

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