Angewandte Chemie International Edition

Cover image for Vol. 52 Issue 17

April 22, 2013

Volume 52, Issue 17

Pages 4495–4693

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Miscellaneous
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. You have free access to this content
      Cover Picture: Chiral Magnesium(II) Binaphtholates as Cooperative Brønsted/Lewis Acid–Base Catalysts for the Highly Enantioselective Addition of Phosphorus Nucleophiles to α,β-Unsaturated Esters and Ketones (Angew. Chem. Int. Ed. 17/2013) (page 4495)

      Dr. Manabu Hatano, Takahiro Horibe and Prof. Dr. Kazuaki Ishihara

      Version of Record online: 8 APR 2013 | DOI: 10.1002/anie.201302124

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      Supramolecular catalysts relying on cooperation between Mg ions and a chelating complex (represented by carp in the picture) were developed by K. Ishihara and co-workers in their Communication on page 4549 ff. The enantioselective 1,4-hydrophosphinylation of α,β-unsaturated esters with diaryl phosphine oxides and 1,2-hydrophosphonylation of α,β-unsaturated ketones with dialkyl phosphites was achieved using chiral 3:2 complexes of (R)-(H8-)BINOLate/MgII ions.

    2. You have free access to this content
      Inside Cover: Alcohol-Promoted Ring-Opening Alkyne Metathesis Polymerization (Angew. Chem. Int. Ed. 17/2013) (page 4496)

      Daniel W. Paley, Danielle F. Sedbrook, Dr. John Decatur, Prof. Felix R. Fischer, Dr. Michael L. Steigerwald and Prof. Colin Nuckolls

      Version of Record online: 9 APR 2013 | DOI: 10.1002/anie.201302115

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      An air-stable, dimeric, crystalline molybdenum propylidyne complex is activated by alcohol to initiate ring-opening alkyne metathesis polymerization (ROAMP) of cyclooctynes, as reported by C. Nuckolls and co-workers in their Communication on page 4591 ff. A mononuclear alcohol adduct was identified by NMR and kinetic studies as a key intermediate in the formation of metathesis-active species. The ROAMP reaction tolerates air, water, and phenolic substrates. Picture design: D. W. Paley.

    3. You have free access to this content
      Inside Back Cover: Boron–Boron Multiple Bond in [B(NHC)]2: Towards Stable and Aromatic [B(NHC)]n Rings (Angew. Chem. Int. Ed. 17/2013) (page 4695)

      Dr. Truong Ba Tai and Prof. Dr. Minh Tho Nguyen

      Version of Record online: 15 APR 2013 | DOI: 10.1002/anie.201302122

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      B,N-heterocyclic compounds undergo photoelimination of an R[BOND]H molecule from a CH2[BOND]BR2 unit in solution and in the solid state, generating highly fluorescent azaborine molecules in high yields. In their Communication on page 4554 ff., S. Wang et al. show that this unusual photoelimination is a convenient method for the production of patterned fluorescent films (see “Queen's” in picture) in the solid state. Background picture by Prof. Veikko Keränen (Rovaniemi, Finland).

    4. You have free access to this content
      Back Cover: Recyclable Mitsunobu Reagents: Catalytic Mitsunobu Reactions with an Iron Catalyst and Atmospheric Oxygen (Angew. Chem. Int. Ed. 17/2013) (page 4696)

      Daisuke Hirose, Dr. Tsuyoshi Taniguchi and Prof. Dr. Hiroyuki Ishibashi

      Version of Record online: 8 APR 2013 | DOI: 10.1002/anie.201302117

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      Ethyl 2-arylhydrazinecarboxylates, which are aerobically oxidized by iron catalysis into the corresponding azo species, can act as recyclable reagents in the Mitsunobu reaction. In their Communication on page 4613 ff., Taniguchi et al. report Mitsunobu reactions using catalytic amounts of these hydrazine reagents and iron phthalocyanine in the presence of air.

  2. Miscellaneous

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

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

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

    1. Top of page
    2. Cover Pictures
    3. Miscellaneous
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. Burkhard König (page 4520)

      Version of Record online: 12 MAR 2013 | DOI: 10.1002/anie.201300671

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      “My favorite food is Indian or Thai. I like refereeing because sometimes the manuscripts are surprisingly good …” This and more about Burkhard König can be found on page 4520.

  6. News

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

    1. Top of page
    2. Cover Pictures
    3. Miscellaneous
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. Alkane C[BOND]H Activation by Single-Site Metal Catalysis. Catalysis by Metal Complexes series, Vol. 38. Edited by Pedro J. Pérez. (pages 4522–4523)

      Ive Hermans

      Version of Record online: 28 MAR 2013 | DOI: 10.1002/anie.201301218

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      Springer, Heidelberg, 2012. 269 pp., hardcover, € 106.95.—ISBN 978-9048136988

  8. Highlight

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

      Organocatalyzed Carbonyl–Olefin Metathesis (pages 4524–4525)

      Dr. Ai-Lan Lee

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/anie.201300678

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      The heat is on: A new [3+2] cycloaddition/cycloreversion strategy allows for catalytic and thermally allowed carbonyl–olefin metathesis (see scheme). This strategy opens opportunities for new developments in the field of carbonyl–olefin metathesis, which traditionally relied on stoichiometric amounts of transition-metal reagents or photochemical promotion.

  9. Review

    1. Top of page
    2. Cover Pictures
    3. Miscellaneous
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. Two-Photon Probes

      From One-Photon to Two-Photon Probes: “Caged” Compounds, Actuators, and Photoswitches (pages 4526–4537)

      Dr. Guillaume Bort, Dr. Thibault Gallavardin, Dr. David Ogden and Dr. Peter I. Dalko

      Version of Record online: 18 FEB 2013 | DOI: 10.1002/anie.201204203

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      A leading light: Molecular systems that can be remotely controlled by light are gaining increasing importance in cell biology and neurosciences because of the spatial and temporal precision that is achievable with laser microscopy. Two-photon excitation has significant advantages over one-photon approaches deep in biological tissues, but the design of “smart” probes compatible with cell physiology is challenging.

  10. Communications

    1. Top of page
    2. Cover Pictures
    3. Miscellaneous
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Review
    11. Communications
    1. Metal–Organic Frameworks

      Tandem Postsynthetic Modification of a Metal–Organic Framework by Thermal Elimination and Subsequent Bromination: Effects on Absorption Properties and Photoluminescence (pages 4538–4543)

      Feng Sun, Zheng Yin, Que-Qiao Wang, Dr. Di Sun, Prof. Dr. Ming-Hua Zeng and Dr. Mohamedally Kurmoo

      Version of Record online: 5 APR 2013 | DOI: 10.1002/anie.201300821

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      Inside and outside: Two consecutive postsynthetic modifications, first an elimination reaction in the channels and then bromination at the surface, were realized in a new hybrid metal–organic framework. The dramatic effects of the different groups in the channels and at the surface were studied using gas sorption and the loading/release of solvent and iodine.

    2. Photochemistry

      Formation of Azaborines by Photoelimination of B,N-Heterocyclic Compounds (pages 4544–4548)

      Jia-Sheng Lu, Dr. Soo-Byung Ko, Nicholas R. Walters, Prof. Dr. Youngjin Kang, Francoise Sauriol and Prof. Dr. Suning Wang

      Version of Record online: 5 APR 2013 | DOI: 10.1002/anie.201300873

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      Highly fluorescent π-conjugated polycyclic azaborines can be prepared from B,N-heterocyclic compounds with a BR2-CH2 unit through the elimination of an R-H molecule (see scheme). These clean photoelimination reactions occur both in solution and in polymers doped with the precursors.

    3. Asymmetric Catalysis

      Chiral Magnesium(II) Binaphtholates as Cooperative Brønsted/Lewis Acid–Base Catalysts for the Highly Enantioselective Addition of Phosphorus Nucleophiles to α,β-Unsaturated Esters and Ketones (pages 4549–4553)

      Dr. Manabu Hatano, Takahiro Horibe and Prof. Dr. Kazuaki Ishihara

      Version of Record online: 13 MAR 2013 | DOI: 10.1002/anie.201300938

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      A little cooperation goes a long way: The cooperative Brønsted/Lewis acid–base supramolecular catalysts formed in situ from simple chiral magnesium(II) binaphtholate aqua complexes promoted the highly enantioselective 1,4-hydrophosphinylation of α,β-unsaturated esters with diaryl phosphine oxides and 1,2-hydrophosphonylation of α,β-unsaturated ketones with dialkyl phosphites (see scheme).

    4. Computational Chemistry

      Boron–Boron Multiple Bond in [B(NHC)]2: Towards Stable and Aromatic [B(NHC)]n Rings (pages 4554–4557)

      Dr. Truong Ba Tai and Prof. Dr. Minh Tho Nguyen

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/anie.201300126

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      Chained up: The π conjugation along B-C-N chains and a shift into a deep valence area of σ molecular orbitals (HOMO−6) are the reasons for the high stability of the dimer [B(NHC)]2 (NHC=N-heterocyclic carbene). The cyclic compounds [B(NHC)]n (see selected MOs for n=6) exhibit structural and aromatic features similar to the corresponding hydrocarbons (CH)n.

    5. Materials Chemistry

      Controlled Doping in Thin-Film Transistors of Large Contorted Aromatic Compounds (pages 4558–4562)

      Dr. Shengxiong Xiao, Dr. Seok Ju Kang, Yu Zhong, Shengguo Zhang, Dr. Amy M. Scott, Dr. Alberto Moscatelli, Prof. Nicholas J. Turro, Dr. Michael L. Steigerwald, Prof. Hexing Li and Prof. Colin Nuckolls

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/anie.201300209

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      Bigger and better: The new thin-film organic material octabenzcircumbiphenyl (OBCB; see scheme) forms an active layer in a field effect transistor, which can be switched simultaneously with two different inputs, that is, electrical bias and protonation.

    6. Biocatalysis

      You have full text access to this OnlineOpen article
      Quantum Chemistry as a Tool in Asymmetric Biocatalysis: Limonene Epoxide Hydrolase Test Case (pages 4563–4567)

      Maria E. S. Lind and Prof. Dr. Fahmi Himo

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/anie.201300594

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      Cluster model: Large active-site models (see figure) are used to investigate the selectivity of limonene epoxide hydrolase, both the wild type and mutants optimized through directed evolution. Good agreement is found between theory and the experimental data, thus demonstrating that the quantum chemical cluster approach can be a powerful tool in the field of asymmetric biocatalysis.

    7. Magnetochemistry

      Ammonia Coordination Introducing a Magnetic Moment in an On-Surface Low-Spin Porphyrin (pages 4568–4571)

      Christian Wäckerlin, Dr. Kartick Tarafder, Jan Girovsky, Jan Nowakowski, Tatjana Hählen, Aneliia Shchyrba, Dr. Dorota Siewert, Dr. Armin Kleibert, Prof. Frithjof Nolting, Prof. Peter M. Oppeneer, Prof. Thomas A. Jung and Prof. Nirmalya Ballav

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/anie.201208028

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      Amazing ammonia: The molecular spin state of NiII porphyrin, supported on a ferromagnetic Co surface, can be reversibly switched between spin-off (S=0) and spin-on (S=1) states upon coordination and decoordination of the gaseous ligand NH3, respectively (see picture). This finding clearly indicates the possible use of the system as a single-molecule-based magnetochemical sensor and in spintronics.

    8. Carbocatalysis

      Polycondensation of Boron- and Nitrogen-Codoped Holey Graphene Monoliths from Molecules: Carbocatalysts for Selective Oxidation (pages 4572–4576)

      Dr. Xin-Hao Li and Prof. Markus Antonietti

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/anie.201209320

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      A simple but powerful chemical process—the copolymerization of biomass (glucose) and boric acid as templated by dicyandiamide (see picture)—was used to fabricate high-quality doped graphene monoliths with through-plane nanopores. The holey graphene monoliths had a high surface area and showed excellent performance as metal-free carbocatalysts for selective oxidation.

    9. Polyoxometalates

      Chiral Heteropoly Blues and Controllable Switching of Achiral Polyoxometalate Clusters (pages 4577–4581)

      Yizhan Wang, Dr. Haolong Li, Che Wu, Yang Yang, Lei Shi and Prof. Dr. Lixin Wu

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/anie.201209497

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      Managing the blues: Chiral heteropoly blues of achiral polyoxometalate clusters were created through an intermolecular interaction with a chiral organic compound. Controllable chiroptical switching of the cluster complexes was possible through reversible photochromism of the polyoxometalates (see picture).

    10. Protein Dynamics

      The Mechanism of Allosteric Coupling in Choline Kinase α1 Revealed by the Action of a Rationally Designed Inhibitor (pages 4582–4586)

      María Sahún-Roncero, Dr. Belén Rubio-Ruiz, Dr. Giorgio Saladino, Dr. Ana Conejo-García, Prof. Antonio Espinosa, Dr. Adrián Velázquez-Campoy, Dr. Francesco Luigi Gervasio, Prof. Antonio Entrena and Dr. Ramon Hurtado-Guerrero

      Version of Record online: 25 FEB 2013 | DOI: 10.1002/anie.201209660

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      Applying a CHOK hold: Combined experimental and computational studies of the binding mode of a rationally designed inhibitor of the dimeric choline kinase α1 (CHOKα1) explain the molecular mechanism of negative cooperativity (see scheme) and how the monomers are connected. The results give insight into how the symmetry of the dimer can be partially conserved despite a lack of conservation in the static crystal structures.

    11. Biocatalysis

      High-Yield Production of Dihydrogen from Xylose by Using a Synthetic Enzyme Cascade in a Cell-Free System (pages 4587–4590)

      Julia S. Martín del Campo, Joseph Rollin, Suwan Myung, You Chun, Sanjeev Chandrayan, Prof. Rodrigo Patiño, Prof. Michael WW Adams and Prof.  Y.-H. Percival Zhang

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/anie.201300766

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      Let enzymes work: H2 was produced from xylose and water in one reactor containing 13 enzymes (red). By using a novel polyphosphate xylulokinase (XK), xylose was converted into H2 and CO2 with approaching 100 % of the theoretical yield. The findings suggest that cell-free biosystems could produce H2 from biomass xylose at low cost. Xu5P=xylulose 5-phosphate, G6P=glucose 6-phosphate.

    12. Alkyne Metathesis

      Alcohol-Promoted Ring-Opening Alkyne Metathesis Polymerization (pages 4591–4594)

      Daniel W. Paley, Danielle F. Sedbrook, Dr. John Decatur, Prof. Felix R. Fischer, Dr. Michael L. Steigerwald and Prof. Colin Nuckolls

      Version of Record online: 8 APR 2013 | DOI: 10.1002/anie.201300758

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      Alcohol is the answer! An inactive, air-stable, dimeric molybdenum alkylidyne complex is activated toward ring-opening alkyne metathesis polymerization (ROAMP) by the addition of methanol. The ROAMP is compatible with water and phenol-containing substrates and with the in situ photochemical generation of alkyne monomers from cyclopropenones.

    13. Siderophores

      Interactions of a Periplasmic Binding Protein with a Tetradentate Siderophore Mimic (pages 4595–4598)

      Daniel J. Raines, Dr. Olga V. Moroz, Prof. Keith S. Wilson and Dr. Anne-K. Duhme-Klair

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/anie.201300751

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      Iron-bound structure: The ferric complex of a tetradentate siderophore mimic was synthesized and co-crystallized with the periplasmic binding protein CeuE of Campylobacter jejuni. In addition to electrostatic and hydrogen-bonding interactions between the binding pocket and the substrate, the structure showed direct coordination of two amino acid side chains to the FeIII center (orange, see figure).

    14. Synthetic Methods

      Gold-Catalyzed Cyclization/Oxidative [3+2] Cycloadditions of 1,5-Enynes with Nitrosobenzenes without Additional Oxidants (pages 4599–4603)

      Chun-Hao Chen, Yen-Ching Tsai and Prof. Dr. Rai-Shung Liu

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/anie.201209850

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      Golden control: The title reaction (see scheme) proceeds with high stereocontrol to generate the heterocyclic products in good yield. Experiments to probe the mechanism were performed.

    15. NMR Spectroscopy

      You have full text access to this OnlineOpen article
      Probing Local Backbone Geometries in Intrinsically Disordered Proteins by Cross-Correlated NMR Relaxation (pages 4604–4606)

      Jan Stanek, Saurabh Saxena, Leonhard Geist, Prof. Robert Konrat and Prof. Wiktor Koźmiński

      Version of Record online: 20 MAR 2013 | DOI: 10.1002/anie.201210005

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      An ultra-high-resolution NMR experiment for the measurement of intraresidue 1H(i)–15N(i)–13C′(i) dipolar–chemical shift anisotropy relaxation interference is employed to extract information about local backbone geometries in intrinsically disordered proteins. The study of tumor suppressor BASP1 revealed a population shift of β-turn geometries at low pH conditions and a compaction of the BASP1 structural ensemble.

    16. Synthetic Methods

      Direct Access to Benzo[b]furans through Palladium-Catalyzed Oxidative Annulation of Phenols and Unactivated Internal Alkynes (pages 4607–4612)

      Malleswara Rao Kuram, M. Bhanuchandra and Dr. Akhila K. Sahoo

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/anie.201210217

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      2,3-Disubstituted benzo[b]furans are prepared in one step from commercially available phenols and readily accessible unactivated internal alkynes (see scheme). This Pd-catalyzed oxidative annulation has a broad substrate scope and allows access to a wide range of benzo[b]furans.

    17. Recyclable Mitsunobu Reagents: Catalytic Mitsunobu Reactions with an Iron Catalyst and Atmospheric Oxygen (pages 4613–4617)

      Daisuke Hirose, Dr. Tsuyoshi Taniguchi and Prof. Dr. Hiroyuki Ishibashi

      Version of Record online: 6 MAR 2013 | DOI: 10.1002/anie.201300153

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      Aerobic recycling: A catalytic amount of a hydrazine reagent is sufficient to promote Mitsunobu reactions in the presence of triphenylphosphine, an iron catalyst, and air. The active form of the catalyst, an azo species, can be readily generated by iron-catalyzed aerobic oxidation. MS=molecular sieves, Pc=phthalocyanine.

      Corrected by:

      Corrigendum: Corrigendum: Recyclable Mitsunobu Reagents: Catalytic Mitsunobu Reactions with an Iron Catalyst and Atmospheric Oxygen

      Vol. 54, Issue 13, 3847, Version of Record online: 16 MAR 2015

    18. Carbon Materials

      Small-Angle Neutron Scattering for In Situ Probing of Ion Adsorption Inside Micropores (pages 4618–4622)

      S. Boukhalfa, L. He, Y. B. Melnichenko and Prof. Gleb Yushin

      Version of Record online: 31 JAN 2013 | DOI: 10.1002/anie.201209141

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      Confined ions: The high penetrating power and sensitivity of neutron scattering to isotope substitution are harnessed to observe changes in the ion concentration in a porous carbon material as a function of the applied potential and the pore size. Depending on the solvent properties and the solvent–pore-wall interactions, either enhanced or reduced ion electroadsorption may take place.

    19. Hydrogen Bonds

      The Nature of Hydrogen Bonding in Protic Ionic Liquids (pages 4623–4627)

      Robert Hayes, Dr. Silvia Imberti, Prof. Gregory G. Warr and Assoc. Prof. Rob Atkin

      Version of Record online: 28 FEB 2013 | DOI: 10.1002/anie.201209273

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      The size, direction, strength, and distribution of hydrogen bonds in several protic ionic liquids (PILs) has been elucidated using neutron diffraction and computer simulation. There is significant variation in PIL hydrogen bond interactions ranging from short and linear to long and bi-/trifurcated. The nature of the PIL's hydrogen bonds reflects its macroscopic properties.

    20. Asymmetric Catalysis

      An Asymmetric Diels–Alder Reaction Catalyzed by Chiral Phosphate Magnesium Complexes: Highly Enantioselective Synthesis of Chiral Spirooxindoles (pages 4628–4632)

      Dr. Guilong Li, Tao Liang, Dr. Lukasz Wojtas and Prof. Dr. Jon C. Antilla

      Version of Record online: 20 MAR 2013 | DOI: 10.1002/anie.201209295

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      Mild Magic: A mild, enantioselective Diels–Alder reaction, catalyzed by a chiral magnesium phosphate species, has been developed for the synthesis of various chiral spirooxindoles. Molecular sieves were found to have a considerable effect when used as additives in this reaction.

    21. Anode Materials

      High Capacity and Rate Capability of Amorphous Phosphorus for Sodium Ion Batteries (pages 4633–4636)

      Dr. Jiangfeng Qian, Dr. Xianyong Wu, Dr. Yuliang Cao, Prof. Xinping Ai and Prof. Hanxi Yang

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/anie.201209689

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      Turning on your P/C: An amorphous phosphorus/carbon (a-P/C) composite was synthesized using simple mechanical ball milling of red phosphorus and conductive carbon powders. This material gave an extraordinarily high sodium ion storage capacity of 1764 mA h g−1 (see graph) with a very high rate capability, showing great promise as a high capacity and high rate anode material for sodium ion batteries.

    22. Synthetic Methods

      Redox Chain Reaction—Indole and Pyrrole Alkylation with Unactivated Secondary Alcohols (pages 4637–4640)

      Xinping Han and Prof. Dr. Jimmy Wu

      Version of Record online: 28 MAR 2013 | DOI: 10.1002/anie.201209810

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      Secondary role: Indole and pyrrole derivatives are alkylated with unactivated secondary aliphatic alcohols by a Brønsted acid-catalyzed redox chain reaction mechanism. Broad functional-group tolerance has been demonstrated and preliminary studies suggest that 1,4-reduction of a putative indolyl carbocation is the dominant mechanistic pathway.

    23. Fluorescent Probes

      Identification of Cystathionine β-Synthase Inhibitors Using a Hydrogen Sulfide Selective Probe (pages 4641–4644)

      Megan K. Thorson, Dr. Tomas Majtan, Prof. Jan P. Kraus and Prof. Amy M. Barrios

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/anie.201300841

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      Buzzing with activity: A hydrogen sulfide selective fluorogenic probe, 7-azido-4-methylcoumarin (AzMC), serves as a highly sensitive assay for cystathionine β-synthase activity, and is suitable for the high-throughput discovery of novel enzyme inhibitors.

    24. Hydroformylation

      Selective Palladium-Catalyzed Hydroformylation of Alkynes to α,β-Unsaturated Aldehydes (pages 4645–4649)

      Xianjie Fang, Dr. Min Zhang, Dr. Ralf Jackstell and Prof. Dr. Matthias Beller

      Version of Record online: 20 MAR 2013 | DOI: 10.1002/anie.201300759

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      Atom-efficient: A selective palladium catalyst system is used for the hydroformylation of alkynes (see picture). In this syngas reaction, various alkynes were smoothly transformed to synthetically interesting α,β-unsaturated aldehydes in good yields with high regio- and stereoselectivity.

    25. Allylic Substitution

      Asymmetric Synthesis of α-Chiral Allylic Silanes by Enantioconvergent γ-Selective Copper(I)-Catalyzed Allylic Silylation (pages 4650–4653)

      Lukas B. Delvos, Dr. Devendra J. Vyas and Prof. Dr. Martin Oestreich

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/anie.201300648

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      Gamma way: Regio- and enantioselective allylic substitution with a silicon nucleophile generated by copper(I)-catalyzed Si[BOND]B bond activation provides direct access to α-chiral allylic silanes from linear acceptors. The enantioconvergent catalysis employing McQuade's six-membered N-heterocyclic-carbene–copper(I) catalyst is applicable to aryl- and alkyl-substituted allylic phosphates (see scheme).

    26. Magnetogenic Probes

      Magnetogenesis under Physiological Conditions with Probes that Report on (Bio-)Chemical Stimuli (pages 4654–4658)

      Faycal Touti, Dr. Philippe Maurin and Prof. Jens Hasserodt

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/anie.201208848

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      Switched on: A molecular concept allows the generation of magnetism in an aqueous sample under the influence of a freshly added (bio-)chemical analyte. The analyte (a chemical reagent or enzyme) triggers the conversion of the probe, a diamagnetic chelate compound, into a paramagnetic compound (see scheme). The two probes prepared are easily accessible iron(II) chelates, and are operative at physiological conditions and/or in serum.

    27. Segmental Density of Polymers

      Is the Universal Law Valid for Branched Polymers? (pages 4659–4663)

      Dr. Albena Lederer, Prof. Dr. Walther Burchard, Dr. Anna Khalyavina, Dr. Peter Lindner and Dr. Ralf Schweins

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/anie.201209228

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      A matter of phis: The size of macromolecules is determined by the “universal calibration” based on the Flory–Fox equation (see scheme). The effect of the segmental density of real branched systems on this equation is investigated. To study this effect, accurately prepared polymers with discrete molecular properties were characterized in detail and precisely evaluated.

    28. Zinc Hydride

      Molecular Zinc Dihydride Stabilized by N-Heterocyclic Carbenes (pages 4664–4667)

      Dr. Arnab Rit, Dr. Thomas P. Spaniol, Prof. Dr. Laurent Maron and Prof. Dr. Jun Okuda

      Version of Record online: 20 MAR 2013 | DOI: 10.1002/anie.201300749

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      Solubility problems solved: The first examples of discrete soluble zinc dihydride adducts with NHC ligands reacted with CO2 to produce formate species and efficiently catalyzed the dehydrocoupling of silanes with methanol. These compounds were characterized both in solution and in the solid state (see picture).

    29. Nanotrough Arrays

      Surface-Assisted Organic Synthesis of Hyperbenzene Nanotroughs (pages 4668–4672)

      Qitang Fan, Cici Wang, Yong Han, Prof. Dr. Junfa Zhu, Priv.-Doz. Dr. Wolfgang Hieringer, Julian Kuttner, Prof. Dr. Gerhard Hilt and Prof. Dr. J. Michael Gottfried

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/anie.201300610

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      A hexagonal macrocycle consisting of 18 phenylene units (hyperbenzene) was synthesized on a Cu(111) surface in ultrahigh vacuum by Ullmann coupling of six 4,4′′-dibromo-m-terphenyl molecules. The large diameter of 21.3 Å and the ability to assemble in arrays makes hyperbenzene an interesting candidate for a nanotrough that could enclose metallic, semiconducting, or molecular quantum dots.

    30. Redox-Active Ligands

      Discovering More Non-Innocence: Triazenido versus Triazenyl Radical Ligand Function, and a Comment on [NO2]n as a “Suspect” Ligand (pages 4673–4675)

      Fabian Ehret, Martina Bubrin, Dr. Stanislav Záliš and Prof. Dr. Wolfgang Kaim

      Version of Record online: 20 MAR 2013 | DOI: 10.1002/anie.201209260

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      The unusual suspects: Depending on co-ligands Ln and the effects of substituents (R), the well-known triazenides [N(NR)2] may act as EPR detectable coordinated triazenyl ligands, [N(NR)2]. (see scheme). They are thus new non-innocent ligands and are related to the hitherto unused non-innocent nitrogen dioxide ligand, [NO2]..

    31. Computer-Based Drug Design

      Drugs by Numbers: Reaction-Driven De Novo Design of Potent and Selective Anticancer Leads (pages 4676–4681)

      Priv.-Doz. Dr. Birgit Spänkuch, Dr. Sarah Keppner, Lisa Lange, Dr. Tiago Rodrigues, Dr. Heiko Zettl, Christian P. Koch, Michael Reutlinger, Dr. Markus Hartenfeller, Dr. Petra Schneider and Prof. Dr. Gisbert Schneider

      Version of Record online: 20 NOV 2012 | DOI: 10.1002/anie.201206897

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      A potent and selective inhibitor of the anticancer target Polo-like kinase 1 was found by computer-based molecular design. This type II kinase inhibitor was synthesized as suggested by the design software DOGS and exhibited significant antiproliferative effects against HeLa cells without affecting nontransformed cells. The study provides a proof-of-concept for reaction-based de novo design as a leading tool for drug discovery.

    32. Ion Channels

      Kinetics of Ion Transport through Supramolecular Channels in Single Crystals (pages 4682–4685)

      Cyrille D. Assouma, Dr. Aurélien Crochet, Yvens Chérémond, Prof. Dr. Bernd Giese and Prof. Dr. Katharina M. Fromm

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/anie.201208195

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      Single-crystal to single-crystal transformations are possible by ion-exchange and transport reactions through supramolecular channels that are composed of crown ether molecules and use trihalide ions as scaffolds. Kinetic measurements of ion transport at different temperatures provide activation energy data and show that a very fast exchange of K+ ions with Na+ ions occurs.

    33. Gold Catalysis

      Rational Design of a Gold Carbene Precursor Complex for a Catalytic Cyclopropanation Reaction (pages 4686–4689)

      David H. Ringger and Prof. Dr. Peter Chen

      Version of Record online: 25 MAR 2013 | DOI: 10.1002/anie.201209569

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      Bridging gas- and solution-phase chemistry: A gold(I) carbene precursor complex has been developed and investigated for catalytic cyclopropanation. Formation of the carbene intermediate was first probed by mass spectrometry, followed by cyclopropanation of p-methoxystyrene in solution. The imidazolylidene leaving group serves as a base generated in situ that is necessary in the putative catalytic cycle.

    34. Protein–RNA Interactions

      Red-Light-Controlled Protein–RNA Crosslinking with a Genetically Encoded Furan (pages 4690–4693)

      M. Sc. Moritz J. Schmidt and Dr. Daniel Summerer

      Version of Record online: 19 MAR 2013 | DOI: 10.1002/anie.201300754

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      Well red: A protein-RNA crosslinker has been genetically encoded that can be controlled with red light (see scheme), thus offering high penetration depths in biological materials. This should enable the discovery and mapping of transient protein–RNA interactions and enable the design of peptide- and protein-based drugs for RNA-targeted photodynamic therapy.

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