Angewandte Chemie International Edition

Cover image for Vol. 51 Issue 36

September 3, 2012

Volume 51, Issue 36

Pages 8903–9184

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Obituary
    8. Book Review
    9. Highlights
    10. Essay
    11. Minireview
    12. Review
    13. Communications
    1. You have free access to this content
      Cover Picture: C[BOND]H Bond Functionalization: Emerging Synthetic Tools for Natural Products and Pharmaceuticals (Angew. Chem. Int. Ed. 36/2012) (page 8903)

      Prof. Dr. Junichiro Yamaguchi, Atsushi D. Yamaguchi and Prof. Dr. Kenichiro Itami

      Version of Record online: 15 AUG 2012 | DOI: 10.1002/anie.201206131

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      The functionalization of C[BOND]H bonds has become an enabling tool in the synthesis of pharmaceutically relevant compounds and biologically active natural products. J. Yamaguchi, A. D. Yamaguchi, and K. Itami show in their Review on page 8960 ff. how it allows the summit (target compounds) to be reached in a most straightforward way. A series of studies not only streamlined the state-of-the-art synthesis of useful molecular entities, but also changed the way chemists plan and execute chemical syntheses.

    2. You have free access to this content
      Inside Cover: Kinetics of the Fischer–Tropsch Reaction (Angew. Chem. Int. Ed. 36/2012) (page 8904)

      Dr. Albert J. Markvoort, Prof. Dr. Rutger A. van Santen, Prof. Dr. Peter A. J. Hilbers and Prof. Dr. Emiel J. M. Hensen

      Version of Record online: 22 AUG 2012 | DOI: 10.1002/anie.201206130

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      In the Fischer–Tropsch synthesis a persisting challenge is the design of a catalyst that maximizes both chain growth and carbon monoxide conversion. In their Communication on page 9015 ff., A. J. Markvoort et al. show that high chain growth and high conversion are achieved on dual reaction center sites, where one reaction center is used for CO dissociation and the other for chain growth. For the carbide mechanism (see picture) only on dual reaction center sites surface poisoning by growing chains can be prevented.

    3. You have free access to this content
      Inside Back Cover: Reconfigurable Three-Dimensional DNA Nanostructures for the Construction of Intracellular Logic Sensors (Angew. Chem. Int. Ed. 36/2012) (page 9185)

      Hao Pei, Le Liang, Guangbao Yao, Dr. Jiang Li, Prof. Qing Huang and Prof. Chunhai Fan

      Version of Record online: 15 AUG 2012 | DOI: 10.1002/anie.201206132

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      Intracellular logic gates are constructed using a series of reconfigurable DNA tetrahedral nanostructures that are responsive to ions, small molecules, and complementary DNA strands. In their Communication on page 9020 ff., C. Fan et al. demonstrate the construction of AND, OR, XOR, and INH logic gates, as well as a complex half-adder operation. They also apply these DNA logic gates in living cells for the intracellular detection of ATP.

    4. You have free access to this content
      Back Cover: Hunting for the Magnesium(I) Species: Formation, Structure, and Reactivity of some Donor-Free Grignard Compounds (Angew. Chem. Int. Ed. 36/2012) (page 9186)

      Tomasz Kruczyński, Dr. Nikolay Pushkarevsky, Dr. Patrick Henke, Dr. Ralf Köppe, Dr. Elke Baum, Prof. Dr. Sergey Konchenko, Prof. Dr. Jerzy Pikies and Prof. Dr. Hansgeorg Schnöckel

      Version of Record online: 22 AUG 2012 | DOI: 10.1002/anie.201206128

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      Even 100 years ago the potential of Grignard compounds had been recognized, leading to a Nobel Prize to F. A. V. Grignard in 1912. Although Grignard reagents are widely used in organic synthesis, the exact nature of the redox process on going from Mg metal via MgI species is still not fully understood. In their Communication on page 9025 ff., H. Schnöckel et al. could show experimentally that MgR/MgX radicals are involved in the formation process of Grignard compounds.

  2. Graphical Abstract

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

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Obituary
    8. Book Review
    9. Highlights
    10. Essay
    11. Minireview
    12. Review
    13. Communications
    1. Michael Tsapatsis (page 8926)

      Version of Record online: 9 MAY 2012 | DOI: 10.1002/anie.201202071

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      “When I was eighteen I wanted to be a chemical engineer. Looking back over my career, I am hopeful, based on the progress achieved so far, that molecular sieve films will become a widespread energy-efficient separation technology. …” This and more about Michael Tsapatsis can be found on page 8926.

  5. News

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

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Obituary
    8. Book Review
    9. Highlights
    10. Essay
    11. Minireview
    12. Review
    13. Communications
    1. Thomas Kauffmann (1924–2012) (page 8928)

      Hans J. Schäfer

      Version of Record online: 6 AUG 2012 | DOI: 10.1002/anie.201205689

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  7. Book Review

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Author Profile
    6. News
    7. Obituary
    8. Book Review
    9. Highlights
    10. Essay
    11. Minireview
    12. Review
    13. Communications
    1. Introduction to Strategies for Organic Synthesis. By Laurie S. Starkey. (page 8929)

      Mark Rizzacasa

      Version of Record online: 6 AUG 2012 | DOI: 10.1002/anie.201204936

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      John Wiley & Sons, Hoboken, 2012. 360 pp., softcover, € 43.90.—ISBN 978-0470484098

  8. Highlights

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

      Catalytic Enantioselective Synthesis of Secondary Alkylboronate Building Blocks With and Without Metals (pages 8930–8932)

      Dr. James A. Bull

      Version of Record online: 23 JUL 2012 | DOI: 10.1002/anie.201203876

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      With or without you: Chiral secondary alkylboronates can now be accessed by highly enantioselective catalytic methods including conjugate addition under metal-free conditions with an NHC catalyst, and also iridium-catalyzed hydrogenation. These methods reinforce the potential of secondary alkylboronates as ideal and universal chiral building blocks for bond formation to sp3 carbon atoms.

    2. Homogeneous Catalysis

      Gold in Total Synthesis: Alkynes as Carbonyl Surrogates (pages 8933–8935)

      Dr. William E. Brenzovich Jr.

      Version of Record online: 13 JUL 2012 | DOI: 10.1002/anie.201204598

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      Fields of gold: Recent developments in the field of gold catalysis, using an alkyne as a carbonyl equivalent is becoming an important chemical transformation, thus providing flexibility in synthetic planning of complex and sensitive natural products. Understanding of the reaction and new catalyst designs are providing new conditions that are amenable for late-stage synthetic intermediates.

  9. Essay

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

      “Black Swan Events” in Organic Synthesis (pages 8936–8949)

      Dr. William A. Nugent

      Version of Record online: 15 AUG 2012 | DOI: 10.1002/anie.201202348

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      When a research area “goes viral”, the event typically occurs in conjunction with a major change in “conventional wisdom”. In retrospect, the literature often contains earlier hints that the original judgment was not correct. These antecedents are referred to as “Black Swan” events. The picture shows research on homogeneous gold catalysis “going viral”.

  10. Minireview

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

      A “Renaissance” in Radical Trifluoromethylation (pages 8950–8958)

      Prof. Dr. Armido Studer

      Version of Record online: 13 AUG 2012 | DOI: 10.1002/anie.201202624

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      A privileged moiety, the CF3 substituent can be found in many drugs, drug candidates, and agrochemicals. This Minireview highlights recent developments in the radical trifluoromethylation of alkenes and arenes. Important older contributions are also discussed.

  11. Review

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

      C[BOND]H Bond Functionalization: Emerging Synthetic Tools for Natural Products and Pharmaceuticals (pages 8960–9009)

      Prof. Dr. Junichiro Yamaguchi, Atsushi D. Yamaguchi and Prof. Dr. Kenichiro Itami

      Version of Record online: 6 AUG 2012 | DOI: 10.1002/anie.201201666

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      The ideal case: The direct functionalization of C[BOND]H bonds in organic compounds has recently emerged as a powerful and ideal method for the formation of carbon–carbon and carbon–heteroatom bonds. This Review provides an overview of C[BOND]H functionalization strategies for the rapid synthesis of biologically active compounds such as natural products and pharmaceutical targets.

  12. Communications

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

      A Metal-Based Inhibitor of Tumor Necrosis Factor-α (pages 9010–9014)

      Dr. Chung-Hang Leung, Hai-Jing Zhong, Hui Yang, Zhen Cheng, Daniel Shiu-Hin Chan, Victor Pui-Yan Ma, Prof. Ruben Abagyan, Dr. Chun-Yuen Wong and Dr. Dik-Lung Ma

      Version of Record online: 13 JUL 2012 | DOI: 10.1002/anie.201202937

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      Staying in the pocket: A cyclometalated iridium(III) biquinoline complex targets the protein–protein interface (see picture; C yellow, N blue, Ir dark green) of the tumor necrosis factor-α (TNF-α) trimer. Molecular-modeling studies confirm the nature of this interaction. Both enantiomers of the iridium complex display comparable in vitro potency to the strongest small-molecule inhibitor of TNF-α.

    2. Heterogeneous Catalysis

      Kinetics of the Fischer–Tropsch Reaction (pages 9015–9019)

      Dr. Albert J. Markvoort, Prof. Dr. Rutger A. van Santen, Prof. Dr. Peter A. J. Hilbers and Prof. Dr. Emiel J. M. Hensen

      Version of Record online: 24 JUL 2012 | DOI: 10.1002/anie.201203282

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      Long carbon chains: Self-assembly of monomeric carbon intermediates into long-chain hydrocarbons on catalytically reactive surface (see picture) was studied when full reversibility of the chain growth is included in the kinetic model. Using Brønsted–Evans–Polanyi relations, the maximum chain growth as a function of the surface reactivity is predicted.

    3. DNA Computing

      Reconfigurable Three-Dimensional DNA Nanostructures for the Construction of Intracellular Logic Sensors (pages 9020–9024)

      Hao Pei, Le Liang, Guangbao Yao, Dr. Jiang Li, Prof. Qing Huang and Prof. Chunhai Fan

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/anie.201202356

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      Right out of the (logic) gate: Logic gates made from 3D DNA nanotetrahedra were constructed that are responsive to various ions, small molecules, and short strands of DNA. By including dynamic sequences in one or more edges of the tetrahedra, a FRET signal can be generated in the manner of AND, OR, XOR, and INH logic gates, as well as a half-adder circuit (see scheme). These DNA logic gates were also applied to intracellular detection of ATP.

    4. Radical Reactions

      Hunting for the Magnesium(I) Species: Formation, Structure, and Reactivity of some Donor-Free Grignard Compounds (pages 9025–9029)

      Tomasz Kruczyński, Dr. Nikolay Pushkarevsky, Dr. Patrick Henke, Dr. Ralf Köppe, Dr. Elke Baum, Prof. Dr. Sergey Konchenko, Prof. Dr. Jerzy Pikies and Prof. Dr. Hansgeorg Schnöckel

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/anie.201204997

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      Magnesium bromide radicals have to be prepared as high-temperature molecules and trapped as a metastable solution because a seemingly simple reduction of donor-free Grignard compounds failed. However, the essential role of magnesium(I) species during the formation of Grignard compounds could be demonstrated experimentally.

    5. Crystal Growth

      Understanding the Formation and Evolution of Ceria Nanoparticles Under Hydrothermal Conditions (pages 9030–9033)

      Christoffer Tyrsted, Kirsten Marie Ørnsbjerg Jensen, Espen Drath Bøjesen, Dr. Nina Lock, Dr. Mogens Christensen, Prof. Dr. Simon J. L. Billinge and Prof. Dr. Bo Brummerstedt Iversen

      Version of Record online: 15 AUG 2012 | DOI: 10.1002/anie.201204747

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      Supercritical growth: The formation and evolution of ceria nanoparticles during hydrothermal synthesis was investigated by in situ total scattering and powder diffraction. The nucleation of pristine crystalline ceria nanoparticles originated from previously unknown cerium dimer complexes. The nanoparticle growth was highly accelerated under supercritical conditions.

    6. Lithium Batteries

      Nano-Structured Phosphorus Composite as High-Capacity Anode Materials for Lithium Batteries (pages 9034–9037)

      Dr. Li Wang, Dr. Xiangming He, Dr. Jianjun Li, Wenting Sun, Dr. Jian Gao, Dr. Jianwei Guo and Prof. Changyin Jiang

      Version of Record online: 2 AUG 2012 | DOI: 10.1002/anie.201204591

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      More than LiP service: The adsorption of red phosphorus into porous carbon provides a composite anode material for lithium-ion batteries. The amorphous nano phosphorus, in the carbon matrix, shows highly reversible lithium storage with high coulombic efficiencies and stable cycling capacity of 750 mAh per gram composite (see picture).

    7. Fullerenes

      Pushing Fullerene Absorption into the Near-IR Region by Conjugately Fusing Oligothiophenes (pages 9038–9041)

      Dr. Zuo Xiao, Gang Ye, Ying Liu, Shan Chen, Dr. Qian Peng, Qiqun Zuo and Prof. Dr. Liming Ding

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/anie.201203981

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      Fusing two in one: The π-electron systems of fullerene and an oligothiophene were conjugately fused by an open-cage process. This led to novel fullerene–oligothiophene chromophores with significantly enhanced light-absorbing capability, which covers a wide spectral range. The fullerene band gap could be tuned to about 1 eV by a chemical approach.

    8. Molecular Devices

      An Air-Stable Low-Bandgap n-Type Organic Polymer Semiconductor Exhibiting Selective Solubility in Perfluorinated Solvents (pages 9042–9046)

      Dr. Youhei Takeda, Dr. Trisha L. Andrew, Dr. Jose M. Lobez, A. Jolene Mork and Prof. Dr. Timothy M. Swager

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/anie.201204066

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      A thin-film transistor: An n-type polymer semiconductor, poly(2,3-bis(perfluorohexyl)thieno[3,4-b]pyrazine), was synthesized through a Pd-catalyzed polycondensation employing a perfluorinated multiphase solvent system. This is the first example of an n-type polymer semiconductor with exclusive solubility in fluorinated solvents. The fabrication of organic field effect transistors containing this new n-type polymer semiconductor is shown (see picture).

    9. Drug Delivery

      Phosphatase-Triggered Fusogenic Liposomes for Cytoplasmic Delivery of Cell-Impermeable Compounds (pages 9047–9051)

      Dr. J. P. Michael Motion, Dr. Juliane Nguyen and Prof. Francis C. Szoka

      Version of Record online: 6 AUG 2012 | DOI: 10.1002/anie.201204198

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      License to fuse! A phosphorylated fusion peptide can mediate membrane fusion when the phosphates (green triangles, see scheme) are removed by phosphatases (blue spheres), delivering the contents of the liposome into the cytosol. This phosphatase-triggered approach may be useful to create target-specific lipid nanocarriers.

    10. Nanosheets

      An Effective Method for the Fabrication of Few-Layer-Thick Inorganic Nanosheets (pages 9052–9056)

      Zhiyuan Zeng, Dr. Ting Sun, Dr. Jixin Zhu, Dr. Xiao Huang, Dr. Zongyou Yin, Dr. Gang Lu, Zhanxi Fan, Prof. Qingyu Yan, Prof. Huey Hoon Hng and Prof. Hua Zhang

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/anie.201204208

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      Intercalation and exfoliation of lithium: Few-layer-thick inorganic nanosheets (BN, NbSe2, WSe2, Sb2Se3, and Bi2Te3) have been prepared from their layered bulk precursors by using a controllable electrochemical lithium intercalation process (see picture). The lithium intercalation conditions, such as cut-off voltage and discharge current, have been systematically studied and optimized to produce high-quality BN and NbSe2 nanosheets.

    11. Rational Drug Design

      Cephalosporin-3′-diazeniumdiolates: Targeted NO-Donor Prodrugs for Dispersing Bacterial Biofilms (pages 9057–9060)

      Dr. Nicolas Barraud, Dr. Bharat G. Kardak, Dr. Nageshwar R. Yepuri, Dr. Robert P. Howlin, Dr. Jeremy S. Webb, Dr. Saul N. Faust, Prof. Staffan Kjelleberg, Dr. Scott A. Rice and Dr. Michael J. Kelso

      Version of Record online: 13 AUG 2012 | DOI: 10.1002/anie.201202414

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      Just say NO to biofilms: NO-donors are used to disperse a bacterial biofilm so that co-administered antibiotics will kill the more susceptible unattached cells. The chemically stable cephalosporin-3′-diazeniumdiolate NO-donor prodrug (see scheme) is activated by bacterial β-lactamases and facilitates this two-step biofilm erradication.

    12. Surface Science

      Adsorbate Alignment in Surface Halogenation: Standing Up is Better than Lying Down (pages 9061–9065)

      Dr. Kai Huang, Dr. Iain R. McNab, Prof. Dr. John C. Polanyi and Dr. Jody (S. Y.) Yang

      Version of Record online: 2 AUG 2012 | DOI: 10.1002/anie.201202772

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      Bromine atom transfer to a silicon surface as a function of physisorbed adsorbate alignment (see picture: left, vertical 1-bromopentane; right, horizontal 1-bromopentane) of 1-bromopropane and 1-bromopentane on Si(111)-7×7 has been studied by STM. In both thermal and electron-induced bromination reactions, the vertical alignment is more reactive.

    13. Reactive Oxygen Species

      Hydrogen Peroxide Induced Activation of Gene Expression in Mammalian Cells using Boronate Estrone Derivatives (pages 9066–9070)

      Jeane M. Govan, Andrew L. McIver, Chad Riggsbee and Prof. Dr. Alexander Deiters

      Version of Record online: 31 JUL 2012 | DOI: 10.1002/anie.201203222

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      Keeping the boron out of the ER: A genetic switch was engineered that activates gene expression in the presence of H2O2 (see scheme). The use of a boronate group on an estrone molecule allows for activation of gene expression through binding of the estrogen receptor only when the boron group is oxidized by H2O2. This sensor is highly sensitive and specific for H2O2.

    14. Cross-Coupling

      C[BOND]O Cross-Coupling of Activated Aryl and Heteroaryl Halides with Aliphatic Alcohols (pages 9071–9074)

      Peter E. Maligres, Jing Li, Shane W. Krska, John D. Schreier and Izzat T. Raheem

      Version of Record online: 6 AUG 2012 | DOI: 10.1002/anie.201203460

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      A robust and general catalyst system facilitates the alkoxylation of activated heteroaryl halides with primary, secondary, and select tertiary alcohols without the need for an excess of either coupling partner (see scheme). This catalyst system displays broad functional-group tolerance and excellent regioselectivity, and is insensitive to the order of reagent addition.

    15. DNA Logic Gates

      Molecular Logic Gates for DNA Analysis: Detection of Rifampin Resistance in M. tuberculosis DNA (pages 9075–9077)

      Evan M. Cornett, Eleanor A. Campbell, George Gulenay, Evan Peterson, Neha Bhaskar and Dr. Dmitry M. Kolpashchikov

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/anie.201203708

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      Elementary, Dr. Watson! A combination of YES and OR logic gates was applied to differentiate between DNA sequences of wild-type and rifampin-resistant (Rifr) Mycobacterium tuberculosis (Mtb) in a multiplex real-time fluorescent assay.

    16. DNA Nanotechnology

      Discovery of the DNA “Genetic Code” for Abiological Gold Nanoparticle Morphologies (pages 9078–9082)

      Dr. Zidong Wang, Longhua Tang, Li Huey Tan, Prof. Dr. Jinghong Li and Prof. Dr. Yi Lu

      Version of Record online: 2 AUG 2012 | DOI: 10.1002/anie.201203716

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      DNA is in control: Different combinations of DNA nucleotides can control the shape and surface roughness of gold nanoparticles during their synthesis. These nanoparticles were synthesized in the presence of either homogenous oligonucleotides or mixed-base oligonucleotides using gold nanoprisms as seeds. The effect of the individual DNA bases and their combinations on shape control are shown in the figure.

    17. Enzyme Substrates

      Profiling of Substrates for Zinc-dependent Lysine Deacylase Enzymes: HDAC3 Exhibits Decrotonylase Activity In Vitro (pages 9083–9087)

      Dr. Andreas S. Madsen and Prof. Christian A. Olsen

      Version of Record online: 13 AUG 2012 | DOI: 10.1002/anie.201203754

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      Systematic screening of the activities of the eleven human zinc-dependent lysine deacylases against a series of fluorogenic substrates (see scheme) as well as kinetic evaluation revealed substrates for screenings of histone deacetylases HDAC10 and HDAC11 at reasonably low enzyme concentrations. Furthermore, HDAC3 in complex with nuclear receptor corepressor 1 (HDAC3–NCoR1) was shown to harbor decrotonylase activity in vitro.

    18. Asymmetric Catalysis

      Enantioselective H-Bond-Directing Approach for Trienamine-mediated Reactions in Asymmetric Synthesis (pages 9088–9092)

      Dr. Łukasz Albrecht, Fabio Cruz Acosta, Dr. Alberto Fraile, Dr. Anna Albrecht, Jannie Christensen and Prof. Dr. Karl Anker Jørgensen

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/anie.201204790

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      Right direction: The presented enantioselective strategy for the preparation of diversely functionalized tetrahydroxanthones is based on a trienamine-mediated cycloaddition between 2,4-dieneals and activated chromones. It is possibile to control the stereochemical outcome of such reactions by employing an H-bond-directing aminocatalyst.

    19. Synthetic Methods

      Baeyer–Villiger Oxidation and Oxidative Cascade Reactions with Aqueous Hydrogen Peroxide Catalyzed by Lipophilic Li[B(C6F5)4] and Ca[B(C6F5)4]2 (pages 9093–9096)

      Dr. Muhammet Uyanik, Daisuke Nakashima and Prof. Dr. Kazuaki Ishihara

      Version of Record online: 15 AUG 2012 | DOI: 10.1002/anie.201204286

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      Efficient and selective: Two lipophilic catalysts were used for Baeyer–Villiger (BV) oxidations to give lactones in high yields (see scheme). Cascade reactions involving this BV oxidation were used to selectively obtain either unsaturated carboxylic acids or hydroxylactones in high yields from β-silyl cyclohexanones.

    20. Phosphorus Complexes

      [Co(η5-P5){η2-P2H(mes)}]2−: A Phospha-Organometallic Complex Obtained by the Transition-Metal-Mediated Activation of the Heptaphosphide Trianion (pages 9097–9100)

      Caroline M. Knapp, Bethan H. Westcott, Melissa A. C. Raybould, Dr. John E. McGrady and Dr. Jose M. Goicoechea

      Version of Record online: 29 JUL 2012 | DOI: 10.1002/anie.201203980

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      A carbon copy: The chemical activation of the heptaphosphide trianion with [Co(PEt2Ph)2(mes)2] (see picture; 1) yields the novel phospha-organometallic complex [Co(η5-P5){η2-P2H(mes)}]2− (2). The reaction product maintains the nuclearity of the parent cluster, but extensive cage fragmentation takes place to yield a diamagnetic “inorganometallic” cobalt complex.

    21. C[BOND]H Activation

      Ligand-Accelerated Activation of Strong C[BOND]H Bonds of Alkanes by a (Salen)ruthenium(VI)–Nitrido Complex (pages 9101–9104)

      Dr. Wai-Lun Man, Dr. William W. Y. Lam, Dr. Hoi-Ki Kwong, Dr. Shek-Man Yiu and Prof. Tai-Chu Lau

      Version of Record online: 31 JUL 2012 | DOI: 10.1002/anie.201204136

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      Kinetic and mechanistic studies on the intermolecular activation of strong C[BOND]H bonds of alkanes by a (salen)ruthenium(VI) nitride were performed. The initial, rate-limiting step, the hydrogen atom transfer (HAT) from the alkane to RuVI[TRIPLE BOND]N, generates RuV[DOUBLE BOND]NH and RC.HCH2R. The following steps involve N-rebound and desaturation.

    22. Oxidative Amination

      α-Amination of Aldehydes Catalyzed by In Situ Generated Hypoiodite (pages 9105–9109)

      Jie-Sheng Tian, Kang Wai Jeffrey Ng, Jiun-Ru Wong and Prof. Teck-Peng Loh

      Version of Record online: 31 JUL 2012 | DOI: 10.1002/anie.201204215

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      The metal-free amination of different aldehydes is catalyzed by hypoiodite, which is generated by employing commercially available sodium percarbonate as the co-oxidant. This approach has several advantages: it is a metal-free oxidation that works under mild reaction conditions; furthermore, it has a wide substrate scope and does not give toxic by-products from the co-oxidant that is used.

    23. Cross-Coupling

      Copper-Catalyzed Cross-Coupling of Functionalized Alkyl Halides and Tosylates with Secondary and Tertiary Alkyl Grignard Reagents (pages 9110–9113)

      Peng Ren, Lucas-Alexandre Stern and Prof. Dr. Xile Hu

      Version of Record online: 31 JUL 2012 | DOI: 10.1002/anie.201204275

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      Added value: A copper-based method is highly efficient for the cross-coupling of alkyl electrophiles with secondary and tertiary alkyl Grignard reagents. The method is distinguished by its broad substrate scope and high functional group tolerance.

    24. Ionic Gels

      One-Step Synthesis of Thermosensitive Nanogels Based on Highly Cross-Linked Poly(ionic liquid)s (pages 9114–9118)

      Dr. Yubing Xiong, Jingjiang Liu, Yujiao Wang, Hong Wang and Prof. Rongmin Wang

      Version of Record online: 2 AUG 2012 | DOI: 10.1002/anie.201202957

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      A gel for all seasons: Thermosensitive nanogels based on highly cross-linked poly(ionic liquid)s (CLPNs) were prepared in one step by the copolymerization of imidazolium-based monomers with cross-linkers in selective solvents. Reversible nanogel–macrogel transitions of CLPNs in methanol could be achieved by changing the temperature (see picture).

    25. Imaging Agents

      Hydrogels Incorporating GdDOTA: Towards Highly Efficient Dual T1/T2 MRI Contrast Agents (pages 9119–9122)

      Dr. Thomas Courant, Dr. Valérie Gaëlle Roullin, Dr. Cyril Cadiou, Dr. Maïté Callewaert, Prof. Marie Christine Andry, Christophe Portefaix, Prof. Christine Hoeffel, Marie Christine de Goltstein, Dr. Marc Port, Dr. Sophie Laurent, Prof. Luce Vander Elst, Prof. Robert Muller, Prof. Michaël Molinari and Prof. Françoise Chuburu

      Version of Record online: 2 AUG 2012 | DOI: 10.1002/anie.201203190

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      Do not tumble dry: Gadolinium-DOTA encapsulated into polysaccharide nanoparticles (GdDOTA⊂NPs) exhibited high relaxivity (r1=101.7 s−1 mM−1 per Gd3+ ion at 37 °C and 20 MHz). This high relaxation rate is due to efficient Gd loading, reduced tumbling of the Gd complex, and the hydrogel nature of the nanoparticles. The efficacy of the nanoparticles as a T1/T2 dual-mode contrast agent was studied in C6 cells (see picture).

    26. Interfaces

      The Formation of Percolative Composites with a High Dielectric Constant and High Conductivity (pages 9123–9127)

      Mingsong Wang, Prof. Jiliang Zhu, Dr. Wenliang Zhu, Bo Zhu, Jing Liu, Prof. Xiaohong Zhu, Yunti Pu, Ping Sun, Zifan Zeng, Xuhai Li, Dr. Daqing Yuan, Dr. Shengyun Zhu and Prof. Giuseppe Pezzotti

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/anie.201203389

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      The dielectric constant and electrical conductivity of a composite of two insulators, poly(1,1-difluoroethylene) (yellow) and K2CO3 (white), increased dramatically near the percolation threshold fc (f=concentration of K2CO3). This intriguing phenomenon can be interpreted in terms of interface percolation caused by the formation of chemically activated interfaces.

    27. Photoelectrolysis

      Hydrogen Production Using a Molybdenum Sulfide Catalyst on a Titanium-Protected n+p-Silicon Photocathode (pages 9128–9131)

      Dr. Brian Seger, Anders B. Laursen, Dr. Peter C. K. Vesborg, Dr. Thomas Pedersen, Prof. Ole Hansen, Prof. Søren Dahl and Prof. Ib Chorkendorff

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/anie.201203585

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      A low-cost substitute: A titanium protection layer on silicon made it possible to use silicon under highly oxidizing conditions without oxidation of the silicon. Molybdenum sulfide was electrodeposited on the Ti-protected n+p-silicon electrode. This electrode was applied as a photocathode for water splitting and showed a greatly enhanced efficiency.

    28. Reactive Intermediates

      Characterization of a Thiolato Iron(III) Peroxy Dianion Complex (pages 9132–9136)

      Dr. Aidan R. McDonald, Dr. Katherine M. Van Heuvelen, Dr. Yisong Guo, Dr. Feifei Li, Prof. Dr. Emile L. Bominaar, Prof. Dr. Eckard Münck and Prof. Dr. Lawrence Que Jr.

      Version of Record online: 6 AUG 2012 | DOI: 10.1002/anie.201203602

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      Nucleophilic oxidant: The reaction between a thiolato iron(II) complex 1 and superoxide in aprotic solvent at −90 °C yields a novel thiolato iron(III) peroxide intermediate 2, which exhibits unusually high nucleophilic reactivity. Compound 2 is an isomer of the thiolato iron(II) superoxide intermediate that is invoked in the reaction between superoxide reductase and superoxide.

    29. Indole Synthesis

      Synthesis of Indoles through Highly Efficient Cascade Reactions of Sulfur Ylides and N-(ortho-Chloromethyl)aryl Amides (pages 9137–9140)

      Qing-Qing Yang, Cong Xiao, Dr. Liang-Qiu Lu, Jing An, Fen Tan, Bin-Jie Li and Prof. Dr. Wen-Jing Xiao

      Version of Record online: 6 AUG 2012 | DOI: 10.1002/anie.201203657

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      Batting the ylides: A simple procedure carried out under mild conditions allows the direct and efficient synthesis of structurally diverse indoles. This approach involves a cascade reaction of sulfur ylides and N-(ortho-chloromethyl)aryl amides (see scheme).

    30. Asymmetric Catalysis

      An Asymmetric Aerobic Aza-Wacker-Type Cyclization: Synthesis of Isoindolinones Bearing Tetrasubstituted Carbon Stereocenters (pages 9141–9145)

      Guoqiang Yang, Chaoren Shen and Prof. Wanbin Zhang

      Version of Record online: 15 AUG 2012 | DOI: 10.1002/anie.201203693

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      It's all in the solvent: An enantioselective variant of an aza-Wacker-type cyclization that gives isoindolinones containing tetrasubstituted carbon centers α to the nitrogen atom has been developed (see scheme; tfa=trifluoroacetate). The use of a highly coordinating solvent is crucial for the activity of the catalyst and the stereoselectivity the reaction (up to 99 % ee).

    31. Photoinduced Electron Transfer

      Room-Temperature Photoinduced Electron Transfer in a Prussian Blue Analogue under Hydrostatic Pressure (pages 9146–9148)

      Dr. Jean-Daniel Cafun, Julien Lejeune, Dr. François Baudelet, Dr. Paul Dumas, Dr. Jean-Paul Itié and Prof. Anne Bleuzen

      Version of Record online: 6 AUG 2012 | DOI: 10.1002/anie.201203943

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      In from the cold: The CoIIIFeII state of a CoFe Prussian blue analogue undergoes a CoIII[BOND]FeII[RIGHTWARDS ARROW](CoII[BOND]FeIII)* electron transfer at room temperature when irradiated by visible light (532 nm; see scheme). This property was confirmed using energy-dispersive X-ray absorption spectroscopy at the Co and Fe K-edges of the piezo-induced CoIIIFeII state.

    32. Noncovalent Interactions

      Evidence for C[BOND]H Hydrogen Bonding in Salts of tert-Butyl Cation (pages 9149–9151)

      Prof.Dr. Evgenii S. Stoyanov, Irina V. Stoyanova, Dr. Fook S. Tham and Prof. Dr. Christopher A Reed

      Version of Record online: 6 AUG 2012 | DOI: 10.1002/anie.201203958

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      Environmentally sensitive: A combination of C[BOND]H⋅⋅⋅⋅anion hydrogen bonding and hyperconjugative charge delocalization explains the sensitivity of the IR spectrum of the tert-butyl cation to its anion (see high-resolution X-ray structure with a CHB11Cl11 counterion). The νCH vibration of the cation scales linearly with the basicity of carborane anions on the νNH scale. The same also holds for the C6H7+ benzenium ion.

    33. Organocatalysis

      α-Selective Organocatalytic Synthesis of 2-Deoxygalactosides (pages 9152–9155)

      Edward I. Balmond, Dr. Diane M. Coe, Dr. M. Carmen Galan and Dr. Eoghan M. McGarrigle

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/anie.201204505

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      Alpha rules: A thiourea acts as an efficient organocatalyst for the glycosylation of protected galactals to form oligosaccharides containing a 2-deoxymonosaccharide moiety (see scheme). The reaction is highly stereoselective for α-linkages and proceeds by way of a syn-addition mechanism.

    34. Biocatalysis

      Redox Self-Sufficient Biocatalyst Network for the Amination of Primary Alcohols (pages 9156–9159)

      Johann H. Sattler, Michael Fuchs, Katharina Tauber, Dr. Francesco G. Mutti, Prof. Dr. Kurt Faber, Dr. Jan Pfeffer, Dr. Thomas Haas and Prof. Dr. Wolfgang Kroutil

      Version of Record online: 9 AUG 2012 | DOI: 10.1002/anie.201204683

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      Driving the machinery: A biocatalytic redox-neutral cascade for the preparation of terminal primary amines from primary alcohols at the expense of ammonia has been established in a one-pot one-step method (see picture). Applying this artificial biocatalyst network, long-chain 1,ω-alkanediols were converted into diamines, which are building blocks for polymers, in up to 99 % conversion.

    35. Natural Products

      Synthetic Studies on Chartelline C: Stereoselective Construction of the Core Skeleton (pages 9160–9163)

      Dr. Kotaro Iwasaki, Rentaro Kanno, Dr. Toshiharu Morimoto, Dr. Tohru Yamashita, Dr. Satoshi Yokoshima and Prof. Tohru Fukuyama

      Version of Record online: 2 AUG 2012 | DOI: 10.1002/anie.201204726

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      What a core-ker! The title synthesis was achieved using a route featuring an intramolecular Mitsunobu reaction of a nosyl amide, stereoselective construction of the β-lactam, and formation of an enamide moiety by selenoxide elimination. The stereochemistry of the alkylation for the formation of the β-lactam was controlled by a secondary hydroxy group on the ten-membered ring. SEM=2-(trimethylsilyl)ethoxymethyl; TBS=tert-butyldimethylsilyl.

      Corrected by:

      Corrigendum: Corrigendum: Synthetic Studies on Chartelline C: Stereoselective Construction of the Core Skeleton

      Vol. 53, Issue 15, 3768, Version of Record online: 3 APR 2014

    36. Nanostructures

      A Yolk–Shell Nanoreactor with a Basic Core and an Acidic Shell for Cascade Reactions (pages 9164–9168)

      Yan Yang, Dr. Xiao Liu, Xiaobo Li, Dr. Jiao Zhao, Dr. Shiyang Bai, Dr. Jian Liu and Prof. Qihua Yang

      Version of Record online: 2 AUG 2012 | DOI: 10.1002/anie.201204829

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      Smart yolk–shell nanoparticles (hollow nanoparticles with a movable core) with an acidic shell and a basic core were fabricated through an organosilane-assisted selective etching method and acted as efficient nanoreactors for catalyzing a deacetalization–Henry cascade reaction with high activity and high selectivity. This strategy is very promising for the design of multifunctional nanoreactors for cascade reactions.

    37. Natural Products

      Total Synthesis of (−)-Quinocarcin by Gold(I)-Catalyzed Regioselective Hydroamination (pages 9169–9172)

      Hiroaki Chiba, Dr. Shinya Oishi, Prof. Dr. Nobutaka Fujii and Prof. Dr. Hiroaki Ohno

      Version of Record online: 13 AUG 2012 | DOI: 10.1002/anie.201205106

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      In control: The novel and enantioselective total synthesis of (−)-quinocarcin includes the highly stereoselective preparation of the 2,5-cis-pyrrolidine by intramolecular amination, a selective substrate-controlled 6-endo-dig intramolecular alkyne hydroamination with a cationic AuI catalyst, and Lewis-acid-mediated ring-opening/halogenation sequence.

    38. Amide Formation

      Facile Synthesis of Sterically Hindered and Electron-Deficient Secondary Amides from Isocyanates (pages 9173–9175)

      Gabriel Schäfer, Coraline Matthey and Prof. Dr. Jeffrey W. Bode

      Version of Record online: 13 AUG 2012 | DOI: 10.1002/anie.201204481

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      The big easy: The direct coupling of Grignard reagents to isocyanates provides a facile and robust solution for the synthesis of sterically hindered and electron-deficient secondary amides. The products are obtained in high yields without the need for excess reagents or chromatographic purification.

    39. Aptamer Affinity Labeling

      Aptamer-Based Affinity Labeling of Proteins (pages 9176–9180)

      Dr. Jan L. Vinkenborg, Prof. Günter Mayer and Prof. Michael Famulok

      Version of Record online: 2 AUG 2012 | DOI: 10.1002/anie.201204174

      Thumbnail image of graphical abstract

      A most able label: Labeled aptamers (see picture) can be cross-linked to their target structures in a light-dependent and highly specific manner as a result of a new strategy termed aptamer-based affinity labeling (ABAL) of proteins. The aptamer–protein complexes can be enriched in vitro, from a cellular lysate and from the surface of living cells, opening new ways to study aptamer interactions in biological contexts.

    40. Photoreactions on Surfaces

      (Bio)Molecular Surface Patterning by Phototriggered Oxime Ligation (pages 9181–9184)

      Thomas Pauloehrl, Dr. Guillaume Delaittre, Dr. Michael Bruns, Maria Meißler, Prof. Dr. Hans G. Börner, Prof. Dr. Martin Bastmeyer and Prof. Dr. Christopher Barner-Kowollik

      Version of Record online: 13 AUG 2012 | DOI: 10.1002/anie.201202684

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      Making light work of ligation: A novel method utilizes light for oxime ligation chemistry. A quantitative, low-energy photodeprotection generates aldehyde, which subsequently reacts with aminooxy moieties. The spatial control allows patterning on surfaces (see scheme) with a fluoro marker and GRGSGR peptide, and can be imaged by time-of-flight secondary-ion mass spectrometry.

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