Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 18

April 26, 2013

Volume 52, Issue 18

Pages 4697–4953

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Obituary
    9. Book Review
    10. Essay
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Cover Picture: Maillard Degradation Pathways of Vitamin C (Angew. Chem. Int. Ed. 18/2013) (page 4697)

      Mareen Smuda and Prof. Dr. Marcus A. Glomb

      Version of Record online: 8 APR 2013 | DOI: 10.1002/anie.201302392

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      Even 80 years after the elucidation of the structure of L-threo-ascorbic acid (vitamin C), the chemistry of this reactive reducing carbohydrate remains exciting. In their Communication on page 4887 ff., M. A. Glomb and M. Smuda report on their investigations into the Maillard degradation pathway, which revealed three major fragmentation mechanisms that lead to carbonyl and dicarbonyl compounds, carboxylic acids, and amide advanced glycation endproducts.

    2. You have free access to this content
      Inside Cover: Conformational Transitions at an S-Layer Growing Boundary Resolved by Cryo-TEM (Angew. Chem. Int. Ed. 18/2013) (page 4698)

      Luis R. Comolli, Cristina E. Siegerist, Seong-Ho Shin, Prof. Carolyn Bertozzi, William Regan, Prof. Alex Zettl and Jim De Yoreo

      Version of Record online: 15 APR 2013 | DOI: 10.1002/anie.201302596

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      Self-assembled S-layer proteins forming the outer membrane on bacterial cells are shown; this rendition is based on AFM images of live Lysinibacillus sphaericus bacteria. In their Communication on page 4829 ff., L. R. Comolli et al. used graphene substrates to examine the structure and assembly of the growing S-layer boundary at high resolution by cryo-TEM. Image courtesy of Zina Deretsky (www.zina-studio.com) based on AFM images by Jinhui Tao, Lawrence Berkeley National Laboratory.

    3. You have free access to this content
      Inside Back Cover: Significant Expansion of the Fluorescent Protein Chromophore through the Genetic Incorporation of a Metal-Chelating Unnatural Amino Acid (Angew. Chem. Int. Ed. 18/2013) (page 4955)

      Xiaohong Liu, Jiasong Li, Cheng Hu, Qing Zhou, Wei Zhang, Meirong Hu, Juanzuo Zhou and Jiangyun Wang

      Version of Record online: 28 MAR 2013 | DOI: 10.1002/anie.201302113

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      A metal-chelating unnatural amino acid (UAA) with an 8-hydroxyquinoline functional group (HqAla) was enzymatically synthesized in one step. In their Communication on page 4805 ff., J. Y. Wang and co-workers show that incorporation of HqAla into fluorescent proteins shifts their emission maxima toward higher wavelengths (red-shifted). This UAA could be applied to engineering metalloproteins and brighter fluorescent proteins, as well as paramagnetic protein NMR spectroscopy.

    4. You have free access to this content
      Back Cover: A Chemical Probe for Lysine Malonylation (Angew. Chem. Int. Ed. 18/2013) (page 4956)

      Xiucong Bao, Qian Zhao, Tangpo Yang, Dr. Yi Man Eva Fung and Prof. Xiang David Li

      Version of Record online: 8 APR 2013 | DOI: 10.1002/anie.201302391

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      Lysine malonylation is a newly identified posttranslational protein modification, whose cellular functions remain largely unknown. In their Communication on page 4883 ff., Y. M. E. Fung, X. D. Li, and co-workers develop the first chemical reporter, MalAM-yne, to detect malonylation of proteins in living cells. The subsequent bioorthogonal conjugation enables the visualization of the dynamics of malonylation and rapid profiling of malonylated proteins.

  2. Editorial

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Obituary
    9. Book Review
    10. Essay
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Editorial: Tenure Track: The Royal Road to Professorship? (pages 4700–4701)

      Prof. Wolfgang A. Herrmann

      Version of Record online: 3 APR 2013 | DOI: 10.1002/anie.201301692

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  3. Graphical Abstract

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

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Obituary
    9. Book Review
    10. Essay
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
  5. News

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

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Obituary
    9. Book Review
    10. Essay
    11. Minireview
    12. Review
    13. Communications
    1. Thomas Ward (page 4722)

      Version of Record online: 20 DEC 2012 | DOI: 10.1002/anie.201208430

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      “I can never resist fresh sushi with a cup of green tea. My greatest achievement has been our three wonderful kids. …” This and more about Thomas Ward can be found on page 4722.

  7. Obituary

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Obituary
    9. Book Review
    10. Essay
    11. Minireview
    12. Review
    13. Communications
    1. Rudolf Wiechert (1928–2013) (page 4723)

      Ekkehard Winterfeldt

      Version of Record online: 26 MAR 2013 | DOI: 10.1002/anie.201301415

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  8. Book Review

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Obituary
    9. Book Review
    10. Essay
    11. Minireview
    12. Review
    13. Communications
    1. Applications of Supramolecular Chemistry. Edited by Hans-Jörg Schneider. (page 4724)

      Ulrich Lüning

      Version of Record online: 3 APR 2013 | DOI: 10.1002/anie.201301525

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      CRC Press, Boca Raton, 2012. 453 pp., hardcover, $ 99.95.—ISBN 978-1439840146

  9. Essay

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Obituary
    9. Book Review
    10. Essay
    11. Minireview
    12. Review
    13. Communications
    1. Attacking N2

      New Approaches to Functionalizing Metal-Coordinated N2 (pages 4726–4732)

      Dr. José G. Andino, Shivnath Mazumder, Dr. Kuntal Pal and Prof. Kenneth G. Caulton

      Version of Record online: 2 APR 2013 | DOI: 10.1002/anie.201209168

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      N2, can do: Converting the refractory molecule N2 into synthetic chemicals is thermodynamically preferred when the derivatizing reactant is a “high-energy molecule”, one with a positive enthalpy of formation. Alkynes and allenes are thus targeted for this purpose (see scheme), and a range of likely products are identified, especially those with N[BOND]N bonds, including bipyrroles.

  10. Minireview

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

      The Photocatalyzed Meerwein Arylation: Classic Reaction of Aryl Diazonium Salts in a New Light (pages 4734–4743)

      M. Sc. Durga Prasad Hari and Prof. Dr. Burkhard König

      Version of Record online: 10 APR 2013 | DOI: 10.1002/anie.201210276

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      Diazonium salts in the spotlight: Photoredox catalysis is an excellent alternative to reactions with stoichiometric reducing reagents for the generation of aryl radicals. In this Minireview, early examples and recent advances of the photoredox chemistry of aryl diazonium salts are discussed.

  11. Review

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

      The N[BOND]H Functional Group in Organometallic Catalysis (pages 4744–4788)

      Prof. Baoguo Zhao, Dr. Zhaobin Han and Prof. Kuiling Ding

      Version of Record online: 7 MAR 2013 | DOI: 10.1002/anie.201204921

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      The “magic” effects of N[BOND]H moieties in organometallic catalysis have been observed in various reaction systems. Recent advances are presented in the development of organometallic catalysts based on the concept of cooperative catalysis by taking the beneficial effect of the NH moiety in the catalyst by catalyst–substrate, ligand–ligand, and catalyst–catalyst interactions.

  12. Communications

    1. Top of page
    2. Cover Pictures
    3. Editorial
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. Obituary
    9. Book Review
    10. Essay
    11. Minireview
    12. Review
    13. Communications
    1. Protein Array in Cells

      You have full text access to this OnlineOpen article
      A Protein-Interaction Array Inside a Living Cell (pages 4790–4794)

      M. Sc. Silke Gandor, Dr. Stephanie Reisewitz, M. Tech. Muthukumaran Venkatachalapathy, Dr. Giuseppe Arrabito, Martina Reibner, Dr. Hendrik Schröder, M. Sc. Katharina Ruf, Prof. Christof M. Niemeyer, Prof. Philippe I. H. Bastiaens and Dr. Leif Dehmelt

      Version of Record online: 4 MAR 2013 | DOI: 10.1002/anie.201209127

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      Taking the bait: Protein-interaction arrays were generated in living cells by the interaction of bait-presenting artificial receptor constructs (bait-PARCs) with micrometer-scaled antibody surface patterns (see figure). This method was applied to simultaneously monitor the interaction kinetics of a prey protein with two distinct bait proteins in individual living cells.

    2. Quantum Simulator

      Hexamethoxyphenalenyl as a Possible Quantum Spin Simulator: An Electronically Stabilized Neutral π Radical with Novel Quantum Coherence Owing to Extremely High Nuclear Spin Degeneracy (pages 4795–4799)

      Dr. Akira Ueda, Dr. Shuichi Suzuki, Kenta Yoshida, Dr. Kozo Fukui, Prof. Dr. Kazunobu Sato, Prof. Dr. Takeji Takui, Prof. Dr. Kazuhiro Nakasuji and Prof. Dr. Yasushi Morita

      Version of Record online: 2 APR 2013 | DOI: 10.1002/anie.201301435

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      A phenalenyl radical with six methoxy groups, which were introduced symmetrically, has been synthesized. The extensively delocalized and highly symmetric electronic-spin system was studied with advanced cw-/pulsed-ESR techniques, thereby giving an experimental model to explore molecular quantum spin simulators with novel quantum coherence attributable to the extremely high degeneracy of the nuclear spin states owing to the eighteen equivalent protons.

    3. Natural Product Synthesis

      Synthesis of Benzoquinone Ansamycin-Inspired Macrocyclic Lactams from Shikimic Acid (pages 4800–4804)

      Valer Jeso, Sarah Iqbal, Pamela Hernandez, Michael D. Cameron, HaJeung Park, Prof. Philip V. LoGrasso and Prof. Glenn C. Micalizio

      Version of Record online: 2 APR 2013 | DOI: 10.1002/anie.201301323

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      One is not like the other: The title approach proceeds by stepwise coupling of three relatively simple substrates. Three natural product-inspired agents are described, one of which has natural product-like toxicity for HeLa and MCF7 cells. It is isoform-selective, thus targeting Hsp90α/β over Grp94, and adopts a conformation similar to that of geldanamycin when complexed with Hsp90.

    4. Protein Engineering

      Significant Expansion of the Fluorescent Protein Chromophore through the Genetic Incorporation of a Metal-Chelating Unnatural Amino Acid (pages 4805–4809)

      Xiaohong Liu, Jiasong Li, Cheng Hu, Qing Zhou, Wei Zhang, Meirong Hu, Juanzuo Zhou and Jiangyun Wang

      Version of Record online: 28 MAR 2013 | DOI: 10.1002/anie.201301307

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      Caught red-shifted: A novel metal-chelating unnatural amino acid with an 8-hydroxyquinoline group (HqAla) can be enzymatically incorporated into GFP (see scheme). Substituting a Tyr residue in the chromophore of FPs with HqAla results in significantly red-shifted excitation and emission maxima. The crystal structure of superfolder GFP bearing HqAla in its chromophore shows the structural basis for these red shifts.

    5. Photocatalysis

      Cu2(OH)PO4, a Near-Infrared-Activated Photocatalyst (pages 4810–4813)

      Gang Wang, Prof. Dr. Baibiao Huang, Xiangchao Ma, Zeyan Wang, Xiaoyan Qin, Prof. Xiaoyang Zhang, Prof. Dr. Ying Dai and Prof. Dr. Myung-Hwan Whangbo

      Version of Record online: 28 MAR 2013 | DOI: 10.1002/anie.201301306

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      Crystal power! Libethenite, Cu2(OH)PO4 (see 4–5 μm×1.5 μm image), absorbs strongly in the near-infrared (NIR) region and is an effective photocatalyst for the decomposition of 2,4-dichlorophenol in aqueous solution under NIR irradiation. This NIR activation of the photocatalyst is due to a facile transfer of photogenerated electrons from the trigonal bipyramidal CuII sites to the adjacent octahedral CuII sites.

    6. Molecular Electroluminescence

      Fluorescence and Phosphorescence of Single C60 Molecules as Stimulated by a Scanning Tunneling Microscope (pages 4814–4817)

      Guangjun Tian and Prof. Dr. Yi Luo

      Version of Record online: 28 MAR 2013 | DOI: 10.1002/anie.201301209

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      Glow-in-the-dark buckyballs: Reproduction of the fluorescence and phosphorescence spectra of single C60 molecules in a scanning tunneling microscope by simulations according to first principles (see picture) revealed the underlying mechanisms and enabled the correct assignment of the spectra.

    7. Multicomponent Reactions

      A Three-Component Palladium-Catalyzed Oxidative C[BOND]C Coupling Reaction: A Domino Process in Two Dimensions (pages 4818–4822)

      Dr. Roshan Y. Nimje, Mikko V. Leskinen and Prof. Dr. Petri M. Pihko

      Version of Record online: 2 APR 2013 | DOI: 10.1002/anie.201300833

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      Easy as ABC… or CBA! Indoles can be selectively functionalized twice by a catalytic oxidative three-component coupling of arylboronates and β-ketoesters. The difference in the rates (see scheme) of the competing processes are amplified under the conditions of the three-component reaction.

    8. Nanocrystal Formation

      Effect of Tertiary and Secondary Phosphines on Low-Temperature Formation of Quantum Dots (pages 4823–4828)

      Dr. Kui Yu, Dr. Xiangyang Liu, Qun Zeng, Donald M. Leek, Dr. Jianying Ouyang, Kenneth Matthew Whitmore, Dr. John A. Ripmeester, Dr. Ye Tao and Prof. Mingli Yang

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/anie.201300568

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      Getting to the TOP of things: The coordination of tri-n-octylphosphine (TOP) instead of diphenylphosphine (DPP) to cadmium oleate (Cd(OA)2) reveals how tertiary and secondary phosphines enhance the yield and reproducibility of the synthesis of nanocrystals by shifting the equilibrium of the reaction to the right (see picture). High Cd-to-Se and Se-to-TOP feed molar ratios facilitate the formation of Se[DOUBLE BOND]DPP by way of Se exchange from TOP to DPP.

    9. Self-Assembly

      Conformational Transitions at an S-Layer Growing Boundary Resolved by Cryo-TEM (pages 4829–4832)

      Luis R. Comolli, Cristina E. Siegerist, Seong-Ho Shin, Prof. Carolyn Bertozzi, William Regan, Prof. Alex Zettl and Jim De Yoreo

      Version of Record online: 5 APR 2013 | DOI: 10.1002/anie.201300543

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      Snapshots of growth: The use of a single graphene layer as the support for S-layer self-assembly of proteins provides an ideal, robust flat surface to image the expanding boundary by flash freezing and cryo-TEM, capturing the conformational states present at the expanding boundary (see figure). Image alignment and averaging provide a view of the steps leading to subunit recruitment and maturation in the self-assembly process.

    10. FeII/FeIII Charge Order

      Sr4Fe6O12: Low-Temperature Fe2+–Fe3+ Charge Order within Pairs of Edge-Linked Tetrahedra (pages 4833–4836)

      Dr. Min Feng Lü, Dr. João C. Waerenborgh and Prof. Colin Greaves

      Version of Record online: 26 MAR 2013 | DOI: 10.1002/anie.201209473

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      Mix and match: Topotactic hydride reduction allows the first synthesis of the fully reduced parent phase, Sr4Fe6O12, of the important family Sr4Fe6O13±δ. The structure provides a rare example of pairs of edge-linked tetrahedra, in this case containing a random arrangement of FeII and FeIII centers at 300 K. On cooling, charge order occurs so that each pair of tetrahedra has one FeII (white) and one FeIII (black) center.

    11. Systems Chemistry

      Selective Assembly and Disassembly of a Water-Soluble Fe10L15 Prism (pages 4837–4840)

      Salvatore Zarra, Dr. Jack K. Clegg and Dr. Jonathan R. Nitschke

      Version of Record online: 26 FEB 2013 | DOI: 10.1002/anie.201209694

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      Survival of the fittest: Two water-soluble metal–organic architectures, a tetrahedron and a pentagonal prism, were selectively assembled from the same building blocks under different reaction conditions. In a mixture of the two, the prism was disassembled upon addition of 4-methoxyaniline to form a mononuclear complex, while leaving the more stable tetrahedral structure intact.

    12. Sustainable Catalysis

      The Electronic States of Rhenium Bipyridyl Electrocatalysts for CO2 Reduction as Revealed by X-ray Absorption Spectroscopy and Computational Quantum Chemistry (pages 4841–4844)

      Dr. Eric E. Benson, Matthew D. Sampson, Dr. Kyle A. Grice, Dr. Jonathan M. Smieja, Jesse D. Froehlich, Dr. Daniel Friebel, Dr. John A. Keith, Prof. Dr. Emily A. Carter, Prof. Dr. Anders Nilsson and Prof. Dr. Clifford P. Kubiak

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/anie.201209911

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      Where are the electrons that allow a highly reduced rhenium bipyridyl catalyst to attack CO2, but not H+? XAS and computational quantum chemistry indicate that the negative charge in [Re(bpy)(CO)3] and [Re(bpy-tBu)(CO)3] is not stored in a localized Re 5d state, but rather in the bipyridine ligand . The active states of this family of catalysts possess formally Re0 metal centers with singly reduced bipyridine ligands.

    13. Self-Assembly

      Supramolecular Thiophene Nanosheets (pages 4845–4848)

      Dr. Yijun Zheng, Haixin Zhou, Dr. Dian Liu, Prof. Dr. George Floudas, Dr. Manfred Wagner, Dr. Kaloian Koynov, Dr. Markus Mezger, Prof. Dr. Hans-Jürgen Butt and Dr. Taichi Ikeda

      Version of Record online: 26 MAR 2013 | DOI: 10.1002/anie.201210090

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      Alternating copolymers consisting of phenyl-capped bithiophene (red units) and oligo(ethylene glycol) hierarchically self-assemble into nanosheets through polymer folding in some organic solvents. The lateral size of the nanosheet is controllable by temperature and concentration of the solution. The nanosheet surface can be chemically modified by using copper-catalyzed Huisgen cycloaddition without disrupting the nanosheet structure.

    14. Xenon Biosensor

      Molecular Imaging of Cancer Cells Using a Bacteriophage-Based 129Xe NMR Biosensor (pages 4849–4853)

      Dr. Krishnan K. Palaniappan, R. Matthew Ramirez, Dr. Vikram S. Bajaj, Prof. Dr. David E. Wemmer, Prof. Dr. Alexander Pines and Prof. Dr. Matthew B. Francis

      Version of Record online: 28 MAR 2013 | DOI: 10.1002/anie.201300170

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      NMR imaging: Filamentous fd bacteriophage expressing antibodies recognizing the epidermal growth factor receptor (EGFR) were modified to incorporate cage-like xenon-binding molecules (CryA). The resulting contrast agent was shown to bind to an EGFR-positive cell line and detected by hyperpolarized 129Xe NMR spectroscopy using chemical exchange saturation transfer (hyperCEST, see picture).

    15. Natural Product Synthesis

      Gallium(III)-Catalyzed Cycloisomerization Approach to the Diterpenoid Alkaloids: Construction of the Core Structure for the Hetidines and Hetisines (pages 4854–4857)

      Amy M. Hamlin, Felipe de Jesus Cortez, David Lapointe and Prof. Richmond Sarpong

      Version of Record online: 26 MAR 2013 | DOI: 10.1002/anie.201209030

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      A versatile core structure has been prepared that should provide a foundation for the syntheses of the hetidine- and hetisine-type diterpenoid alkaloids. The synthesis of the caged polycyclic core structure, which features nine contiguous stereocenters, utilizes a GaIII-catalyzed cycloisomerization of an alkynyl indene as well as a Michael/aldol sequence to build the bicyclo[2.2.2] framework.

    16. Protein Lipidation

      Synthesis of Autophagosomal Marker Protein LC3-II under Detergent-Free Conditions (pages 4858–4862)

      Yi-Chao Huang, Prof. Dr. Yi-Ming Li, Dr. Yang Chen, Man Pan, Yi-Tong Li, Prof. Dr. Li Yu, Prof. Qing-Xiang Guo and Prof. Dr. Lei Liu

      Version of Record online: 2 APR 2013 | DOI: 10.1002/anie.201209523

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      Just add oil: A new detergent-free method was developed to synthesize lipidated proteins using a light-activatable solubilizing side chain (in dashed circle, see scheme) to assist the ligation of the lipopeptides. This method allows the efficient preparation of a phosphatidylethanolamine-conjugated autophagosomal marker protein (LC3-II) as well as labeled derivatives of LC3-II, which can be used to study autophagy regulation.

    17. Main-Group Elements

      Assembly of a cyclo-Tetrastibinotetraphosphonium Tetracation by Reductive Elimination (pages 4863–4866)

      Saurabh S. Chitnis, Dr. Yuen-Ying Carpenter, Prof. Neil Burford, Dr. Robert McDonald and Dr. Michael J. Ferguson

      Version of Record online: 26 MAR 2013 | DOI: 10.1002/anie.201210012

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      Square deal: Reactions of SbF3 with Me3SiOSO2CF3 produce Sb3+ and [Sb-F]2+ cations, which form complexes with two or three Me3P ligands. Subsequent reductive elimination of diphosphonium or fluorophosphonium cations from the complexes give the folded square cyclo-[(Me3P)4Sb4][OTf]4. Formation of the tetracation framework reveals new redox chemistry for Sb.

    18. Crystal Growth

      Calcite Crystal Growth by a Solid-State Transformation of Stabilized Amorphous Calcium Carbonate Nanospheres in a Hydrogel (pages 4867–4870)

      Assaf Gal, Dr. Wouter Habraken, Dvir Gur, Prof. Peter Fratzl, Prof. Steve Weiner and Prof. Lia Addadi

      Version of Record online: 4 APR 2013 | DOI: 10.1002/anie.201210329

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      An ugly duckling grows into a swan: Many organisms grow their crystalline mineral phases through the secondary nucleation of nanospheres made of an amorphous precursor phase. Stable amorphous calcium carbonate biominerals were used to induce a similar transformation in vitro. The amorphous nanospheres underwent a solid-phase transformation that resulted in highly ordered calcite crystals composed of aggregated particles (see SEM image).

    19. Polycyclic Aromatic Hydrocarbons

      Taming Hot CF3 Radicals: Incrementally Tuned Families of Polyarene Electron Acceptors for Air-Stable Molecular Optoelectronics (pages 4871–4874)

      Dr. Igor V. Kuvychko, Karlee P. Castro, S. H. M. Deng, Dr. Xue-Bin Wang, Prof. Steven H. Strauss and Dr. Olga V. Boltalina

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/anie.201300085

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      A regioselective, solvent-, and catalyst-free method for the perfluoroalkylation of polycyclic aromatic hydrocarbons (PAHs) with CF3I was used to synthesize air-stable organic electron acceptors (PAH(CF3)n). The gas-phase electron affinities of these compounds correlate to the number of CF3 groups. The number and orientation of the CF3 groups also influenced the π–π stacking and crystalline morphologies of these compounds.

    20. Energetic Materials

      Synthesis and Characterization of a Stable, Catenated N11 Energetic Salt (pages 4875–4877)

      Yongxing Tang, Dr. Hongwei Yang, Bo Wu, Xuehai Ju, Chunxu Lu and Prof. Guangbin Cheng

      Version of Record online: 2 APR 2013 | DOI: 10.1002/anie.201300117

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      A nitrogen-rich energetic salt containing the longest reported nitrogen chain (N11), was obtained by an azo coupling reaction from 1,5-diaminotetrazole. This is the first example of an azo reaction between an N[BOND]NH2 diazonium salt and an amine derivative. The product structure was confirmed by X-ray crystallography, and its physical and explosive properties were characterized.

    21. Asymmetric Synthesis

      Catalytic Asymmetric Synthesis of Cyclic Ethers Containing an α-Tetrasubstituted Stereocenter (pages 4878–4882)

      Nick Cox, Mycah R. Uehling, Karl T. Haelsig and Gojko Lalic

      Version of Record online: 8 APR 2013 | DOI: 10.1002/anie.201300174

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      'Ether' furan or pyran: The exo-selective cyclization of enantioenriched allenols is accomplished with high chirality transfer using as little as 0.02 mol % of a gold catalyst. The new method is effective in the synthesis of a wide range of enantioenriched cyclic ethers, which are prepared in excellent yields in three steps from readily available propargylic phosphates.

    22. Protein Modifications

      A Chemical Probe for Lysine Malonylation (pages 4883–4886)

      Xiucong Bao, Qian Zhao, Tangpo Yang, Dr. Yi Man Eva Fung and Prof. Xiang David Li

      Version of Record online: 26 MAR 2013 | DOI: 10.1002/anie.201300252

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      Tag! You′re it! MalAM-yne is a chemical reporter for malonylation of lysines within proteins (see scheme), a newly identified posttranslational modification. MalAM-yne is cell-permeable and metabolically incorporated into proteins in living cells. Subsequent bioorthogonal tag conjugation allows the fluorescent visualization of cellular malonylation and profiling of malonylated proteins.

    23. Vitamin C Degradation

      Maillard Degradation Pathways of Vitamin C (pages 4887–4891)

      Mareen Smuda and Prof. Dr. Marcus A. Glomb

      Version of Record online: 28 MAR 2013 | DOI: 10.1002/anie.201300399

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      Degradation mechanisms: 75 % of the Maillard degradation pathways of ascorbic acid can be explained by oxidative α fragmentation (31 %), β cleavage (32 %), and decarboxylation from hydrate/hemiaminal intermediates (12 %), which lead to carbonyl and dicarbonyl compounds, carboxylic acids, and amide advanced glycation endproducts. The results are a major step forward in the understanding of changes occurring in systems containing vitamin C.

    24. Synthetic Methods

      Aerobic Synthesis of Pyrroles and Dihydropyrroles from Imines: Palladium(II)-Catalyzed Intramolecular C[BOND]H Dehydrogenative Cyclization (pages 4892–4896)

      Dr. Zhuangzhi Shi, Mamta Suri and Prof. Dr. Frank Glorius

      Version of Record online: 8 APR 2013 | DOI: 10.1002/anie.201300477

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      sp3ectacularly mild! An efficient PdII-catalyzed intramolecular dehydrogenative cyclization of imines affords (dihydro)pyrrole products using molecular oxygen as the sole oxidant. This mild formal sp3-C[BOND]H functionalization allows rapid and atom-economical assembly of (dihydro)pyrrole rings from inexpensive and readily available allylamines and ketones. A broad range of functional groups are tolerated.

    25. Asymmetric Auto-Tandem Catalysis

      Asymmetric Auto-Tandem Catalysis with a Planar-Chiral Ruthenium Complex: Sequential Allylic Amidation and Atom-Transfer Radical Cyclization (pages 4897–4901)

      Naoya Kanbayashi, Dr. Kazuhiro Takenaka, Dr. Taka-aki Okamura and Prof. Kiyotaka Onitsuka

      Version of Record online: 28 MAR 2013 | DOI: 10.1002/anie.201300485

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      Ru does it all: A novel example of an asymmetric auto-tandem reaction catalyzed by a planar-chiral cyclopentadienyl–ruthenium complex is described. The reaction of allylic chloride with α-haloamides provides synthetically useful, diastereomerically and enantiomerically enriched γ-lactams with multiple stereogenic centers through one-pot sequential allylic amidation/atom-transfer radical cyclization. PG=protecting group.

    26. Synthetic Methods

      Intramolecular Larock Indole Synthesis: Preparation of 3,4-Fused Tricyclic Indoles and Total Synthesis of Fargesine (pages 4902–4905)

      Dong Shan, Yan Gao and Prof. Yanxing Jia

      Version of Record online: 20 MAR 2013 | DOI: 10.1002/anie.201300571

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      Core strength: A new and general strategy for the construction of 3,4-fused tricyclic indoles, which are the core structure of numerous natural products and bioactive molecules, has been developed. The method involves a one-step intramolecular Larock indolization and was successfully applied to the first total synthesis of fargesine.

    27. Cross-Coupling

      Arene CH[BOND]O Hydrogen Bonding: A Stereocontrolling Tool in Palladium-Catalyzed Arylation and Vinylation of Ketones (pages 4906–4911)

      Dr. Zhiyan Huang, Li Hui Lim, Dr. Zuliang Chen, Dr. Yongxin Li, Feng Zhou, Prof. Dr. Haibin Su and Prof. Dr. Jianrong (Steve) Zhou

      Version of Record online: 3 APR 2013 | DOI: 10.1002/anie.201300621

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      Weak is powerful: For the arylation of tin enolates, the palladium catalyst engages in weak CH[BOND]O hydrogen bonds to control stereoselectivity (see scheme). Similar catalysts capable of NH[BOND]O hydrogen bonding also works well.

    28. Contracted Porphyrinoids

      10-Heterocorroles: Ring-Contracted Porphyrinoids with Fine-Tuned Aromatic and Metal-Binding Properties (pages 4912–4915)

      Dimitri Sakow, Birte Böker, Dr. Kai Brandhorst, Dr. Olaf Burghaus and Prof. Dr. Martin Bröring

      Version of Record online: 8 APR 2013 | DOI: 10.1002/anie.201300757

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      A homologous series of ring-contracted corrinoids, the 10-heterocorroles H2(XCor), is now available as the free-base ligand set. While the higher homologues, 10-thia- and 10-selenacorrole, show a porphyrin-like spectroscopic behavior, 10-oxacorrole displays lower aromatic character and has the smallest N4 cavity of all free-base porphyrinoids synthesized so far, smaller even than those of corrole and porphycene ligands (see picture).

    29. Metallomics

      Identification of Metal-Associated Proteins in Cells by Using Continuous-Flow Gel Electrophoresis and Inductively Coupled Plasma Mass Spectrometry (pages 4916–4920)

      Dr. Ligang Hu, Dr. Tianfan Cheng, Dr. Bin He, Dr. Lu Li, Yuchuan Wang, Yau-Tsz Lai, Prof. Guibin Jiang and Prof. Hongzhe Sun

      Version of Record online: 2 APR 2013 | DOI: 10.1002/anie.201300794

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      Metal detector: The title strategy provides a new way for rapid profiling of the metal-associated proteins on a proteome- and metallome-wide scale. The technique was applied to identify protein targets of a bismuth-based drug in Helicobacter pylori and to study the metal binding of the protein SlyD, which is a member of the FK506-binding protein family, in E. coli.

    30. Single-Molecule Magnets

      Single-Molecule Magnetism in a Single-Ion Triamidoamine Uranium(V) Terminal Mono-Oxo Complex (pages 4921–4924)

      David M. King, Dr. Floriana Tuna, Dr. Jonathan McMaster, Dr. William Lewis, Prof. Alexander J. Blake, Prof. Eric J. L. McInnes and Dr. Stephen T. Liddle

      Version of Record online: 8 APR 2013 | DOI: 10.1002/anie.201301007

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      Single-molecule magnets: Straightforward oxidation of a triamidoamine uranium(III) complex with trimethyl-N-oxide affords a uranium(V) terminal mono-oxo complex which is the first clear-cut example of a uranium(V) single-molecule magnet (SMM). This monometallic complex unambiguously shows that a strongly axially ligated and thus anisotropic ligand field can be used to overcome the limited magnetic anisotropy of uranium(V).

    31. Asymmetric Transfer Hydrogenation

      Ruthenium-Catalyzed Asymmetric Transfer Hydrogenation of 1-Aryl-Substituted Dihydroisoquinolines: Access to Valuable Chiral 1-Aryl-Tetrahydroisoquinoline Scaffolds (pages 4925–4928)

      Zi Wu, Marc Perez, Dr. Michelangelo Scalone, Dr. Tahar Ayad and Dr. Virginie Ratovelomanana-Vidal

      Version of Record online: 26 MAR 2013 | DOI: 10.1002/anie.201301134

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      Give me an H! Give me another H! The first general and highly enantioselective Ru-catalyzed transfer hydrogenation of a wide range of 1-aryl-substituted 1,2,3,4-dihydroisoquinolines is described. This atom-economic reaction proceeds under mild conditions, allowing rapid access to the corresponding biologically relevant 1-aryl-tetrahydroisoquinoline derivatives, in high yields and enantioselectivities of up to 99 %.

    32. Synthetic Methods

      Iodine-Catalyzed Regioselective Sulfenylation of Indoles with Sulfonyl Hydrazides (pages 4929–4932)

      Fu-Lai Yang and Prof. Dr. Shi-Kai Tian

      Version of Record online: 28 MAR 2013 | DOI: 10.1002/anie.201301437

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      New S in town: Sulfonyl hydrazides smoothly undergo sulfenylation with indoles in the presence of 10 mol % I2 to give structurally diverse indole thioethers in moderate to excellent yields with extremely high regioselectivity. This study paves the way for the use of sulfonyl hydrazides as unique sulfur electrophiles in chemical synthesis.

    33. Arene Functionalization

      Regioselective Threefold Aromatic Substitution of Benzoic Acid Derivatives by Dearomatization, Regioselective Functionalization, and Rearomatization (pages 4933–4936)

      Eva Koch and Prof. Dr. Armido Studer

      Version of Record online: 26 MAR 2013 | DOI: 10.1002/anie.201300259

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      Ipso, meta, and para: Benzoic acid derivatives can be highly regioselectively substituted at the ipso, meta, and para positions. The reaction sequence comprises an alkylative Birch reduction, a 4-alkylation, a palladium-catalyzed γ-arylation, and an oxidative rearomatization (see scheme). All the reactions are robust and experimentally easy to conduct.

    34. Polyhalogen Anions

      Structural Evidence for Undecabromide [Br11] (pages 4937–4940)

      Dipl.-Chem. Heike Haller, B. Sc. Jan Schröder and Dr. Sebastian Riedel

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/anie.201209928

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      Spreading the charge: Besides iodine, few of the polyhalogen anions have been structurally characterized. Remarkably, the highest known ratio of elements-to-charge has now been found in the undecabromide [Br11]. This new polybromide monoanion has been prepared in pure halogen and was structurally characterized by single-crystal X-ray diffraction, Raman spectroscopy (see picture), and quantum-chemical methods.

    35. Carbene Complexes

      Unusual Tilted Carbene Coordination in Carbene Complexes of Gallium(I) and Indium(I) (pages 4941–4944)

      Alexander Higelin, Sarah Keller, Christian Göhringer, Prof. Cameron Jones and Prof. Dr. Ingo Krossing

      Version of Record online: 2 APR 2013 | DOI: 10.1002/anie.201209757

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      Ga,In insights: A general explanation for the unusual tilted coordination mode of undisturbed gallium(I) and indium(I) carbene complexes of the weakly coordinating anion [Al(ORF)4] (RF=C(CF3)3) is given, which is based on the experimental structures. The results are supported by extensive DFT studies.

    36. Cross-Coupling

      Ligand-Accelerated Iron- and Cobalt-Catalyzed Cross-Coupling Reactions between N-Heteroaryl Halides and Aryl Magnesium Reagents (pages 4945–4949)

      Dipl.-Chem. Olesya M. Kuzmina, Dipl.-Chem. Andreas K. Steib, Dr. John T. Markiewicz, Dr. Dietmar Flubacher and Prof. Dr. Paul Knochel

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/anie.201210235

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      Quinoline and isoquinoline dramatically increase the rate and yield of Fe- and Co-catalyzed cross-coupling reactions. This new catalytic process extends the scope of such cross-coupling reactions to include complex functional groups and allows heteroaryl–heteroaryl bond formation to occur.

    37. Electron Transfer

      You have full text access to this OnlineOpen article
      The Flavoprotein Dodecin as a Redox Probe for Electron Transfer through DNA (pages 4950–4953)

      Dr. Yaming Yu, Dr. Björn Heidel, Tamara Lourdes Parapugna, Sabine Wenderhold-Reeb, Dr. Bo Song, Prof. Dr. Holger Schönherr, Prof. Dr. Martin Grininger and Dr. Gilbert Nöll

      Version of Record online: 26 MAR 2013 | DOI: 10.1002/anie.201208987

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      Flavin away: Dodecin binds oxidized flavins, whereas reduction of the bound flavin induces dissociation of the holoprotein into apododecin and free flavins. The stepwise reconstitution of dodecin on flavin-terminated ds-DNA monolayers showed that although electrochemical flavin reduction (i.e. electron transfer through DNA) was not possible, apododecin (gray circles) could be released by chemical reduction (see scheme).

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