Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 17

April 22, 2014

Volume 53, Issue 17

Pages 4251–4493

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. You have free access to this content
      Cover Picture: Short Chemoenzymatic Total Synthesis of ent-Hydromorphone: An Oxidative Dearomatization/Intramolecular [4+2] Cycloaddition/Amination Sequence (Angew. Chem. Int. Ed. 17/2014) (page 4251)

      Vimal Varghese and Prof. Tomas Hudlicky

      Version of Record online: 25 MAR 2014 | DOI: 10.1002/anie.201401117

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      A 12-step chemoenzymatic total synthesisof ent-hydromorphone from β-bromoethylbenzene is described by T. Hudlicky and V. Varghese in their Communication on page 4355 ff. The key steps consist of enzymatic dihydroxylation, Mitsunobu coupling, and oxidative dearomatization followed by intramolecular [4+2] cycloaddition. This approach holds potential for further optimization of morphine alkaloid syntheses. We acknowledge the legendary efforts of the chemists pictured, who dedicated their careers to the chemistry of morphine. Cover design: Dennis Ceci, Tomas Hudlicky, Jordan Froese (Brock University).

    2. You have free access to this content
      Inside Cover: Identification and X-ray Co-crystal Structure of a Small-Molecule Activator of LFA-1-ICAM-1 Binding (Angew. Chem. Int. Ed. 17/2014) (page 4252)

      Dr. Martin Hintersteiner, Dr. Jörg Kallen, Mario Schmied, Christine Graf, Dr. Thomas Jung, Gemma Mudd, Dr. Steven Shave, Dr. Hubert Gstach and Prof. Manfred Auer

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201401110

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      The immune response regulating the protein–protein interaction of the integrin leucocyte function associated antigen 1 and intercellular adhesion molecule 1 is allosterically enhanced by the binding of IBE-667 to a remote site on LFA-1. M. Hintersteiner, M. Auer, and co-workers show in their Communication on page 4322 ff. that the identification of IBE-667 can be achieved through a combinatorial library screening approach with several techniques.

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      Inside Back Cover: A Convergent Total Synthesis of the Telomerase Inhibitor (±)-γ-Rubromycin (Angew. Chem. Int. Ed. 17/2014) (page 4495)

      Dr. Michael Wilsdorf and Prof. Dr. Hans-Ulrich Reissig

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201401119

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      Silicon in, silicon out could be the caption for the convergent total synthesis of the telomerase inhibitor (±)-γ-rubromycin reported by M. Wilsdorf and H.-U. Reissig in their Communication on page 4332 ff. They combine three highly functionalized building blocks through selective organometallic chemistry and a silyl-substituted C3 building block plays a key role. Three acid-promoted reactions serve to generate the sensitive spiroketal natural product under desilylation. Graphic courtesy of Dr. Daniel Trawney.

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      Back Cover: A Photo-annealing Approach for Building Functional Polymer Layers on Paper (Angew. Chem. Int. Ed. 17/2014) (page 4496)

      Qiuping Qian, Jian Wang, Prof. Feng Yan and Prof. Yapei Wang

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201401118

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      A photo-annealing approach was developed for building functional polymer layers on paper. In their Communication on page 4465 ff., Y. Wang and co-workers show that conducting polyaniline with the ability to undergo photothermal conversion can be annealed by near-infrared light. The porous structure is retained in the annealed polymer but it becomes insulating and hydrophobic. The asymmetric paper functions as a “water diode” and selective photo-annealing produces patterned conductive arrays.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. You have free access to this content
      Frontispiece: Probing Transient Conformational States of Proteins by Solid-State R Relaxation-Dispersion NMR Spectroscopy

      Dr. Peixiang Ma, Jens D. Haller, Jérémy Zajakala, Dr. Pavel Macek, Dr. Astrid C. Sivertsen, Prof. Dr. Dieter Willbold, Dr. Jérôme Boisbouvier and Dr. Paul Schanda

      Version of Record online: 17 APR 2014 | DOI: 10.1002/anie.201481771

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      In their Communication on page 4312 ff., P. Schanda et al. describe an NMR method used to probe conformational states of proteins. Information about the exchange kinetics, relative populations, and structures of the short-lived state can be obtained.

  3. Graphical Abstract

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

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. Michael G. Organ (page 4272)

      Version of Record online: 11 DEC 2013 | DOI: 10.1002/anie.201310128

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      “My favorite piece of research is the hunt for the polio vaccine. If I were not a scientist, I would be a farmer …” This and more about Michael G. Organ can be found on page 4272.

  6. News

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. News
    6. Author Profile
    7. News
    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. Nanomachines. Fundamentals and Applications. By Joseph Wang. (pages 4274–4275)

      Alberto Credi

      Version of Record online: 12 MAR 2014 | DOI: 10.1002/anie.201311274

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      Wiley-VCH, Weinheim, 2013. 160 pp., softcover, € 39.90.—ISBN 978-3527331208

  8. Highlight

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

      A Scalable Rhodium-Catalyzed Intermolecular Aziridination Reaction (pages 4278–4280)

      David T. Smith and Prof. Jon T. Njardarson

      Version of Record online: 5 MAR 2014 | DOI: 10.1002/anie.201400502

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      The amine has landed! By employing the rhodium catalyst [Rh2(esp)2] in the presence of a readily available amine source (DPH), unactivated and styrene-type olefins can now be stereospecifally transformed, in high yields at room temperature, into valuable NH aziridine products. esp=α,α,α′,α′-tetramethyl-1,3-benzenedipropionic acid.

  9. Minireview

    1. Top of page
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    3. Frontispiece
    4. Graphical Abstract
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    8. Book Review
    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. Copper Oxo Complexes

      Molecular CuII-O-CuII Complexes: Still Waters Run Deep (pages 4282–4293)

      Dr. Peter Haack and Prof. Dr. Christian Limberg

      Version of Record online: 11 MAR 2014 | DOI: 10.1002/anie.201309505

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      Cu-ltivating new areas: Complexes featuring CuII-O-CuII units do not have a developed chemistry. Recently, however, findings suggest such Cu2O units are the methane-oxidizing species of heterogeneous catalysts and are relevant in biological methane monoxygenation, too. This Minireview outlines the spectroscopy, the structures, and reactivities of the few examples reported to date.

  10. Review

    1. Top of page
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    9. Highlight
    10. Minireview
    11. Review
    12. Communications
    1. Bioorganometallic Chemistry

      Bioorganometallic Chemistry with IspG and IspH: Structure, Function, and Inhibition of the [Fe4S4] Proteins Involved in Isoprenoid Biosynthesis (pages 4294–4310)

      Dr. Weixue Wang and Prof. Dr. Eric Oldfield

      Version of Record online: 31 JAN 2014 | DOI: 10.1002/anie.201306712

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      A mission based on inside information: The methylerythritol phosphate pathway is an attractive anti-infective drug target. The last two enzymes of this pathway, IspG and IspH, are [Fe4S4] proteins that catalyze 2 H+/2 e dehydroxylation reactions. Recent progress in the elucidation of their biosynthetic mechanisms opens up new routes to the design of inhibitors that target these [Fe4S4] enzymes.

  11. Communications

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

      You have full text access to this OnlineOpen article
      Probing Transient Conformational States of Proteins by Solid-State R Relaxation-Dispersion NMR Spectroscopy (pages 4312–4317)

      Dr. Peixiang Ma, Jens D. Haller, Jérémy Zajakala, Dr. Pavel Macek, Dr. Astrid C. Sivertsen, Prof. Dr. Dieter Willbold, Dr. Jérôme Boisbouvier and Dr. Paul Schanda

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201311275

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      Functionally relevant states of proteins are often only short-lived, and thus difficult to detect. Relaxation-dispersion experiments in magic-angle-spinning solid-state NMR spectroscopy provide access to such transient states. Information about the exchange kinetics, relative populations, and structures of the short-lived state can be obtained.

    2. Giant Diamagnetism

      Anomalous Diamagnetic Susceptibility in 13-Atom Platinum Nanocluster Superatoms (pages 4318–4321)

      Prof. Emil Roduner, Dr. Christopher Jensen, Prof. Joris van Slageren, Dr. Rainer A. Rakoczy, Dr. Oliver Larlus and Prof. Michael Hunger

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201310637

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      As predicted: The diamagnetic susceptibility per atom of hydride-coated {Pt13} nanoclusters supported by a zeolite, exceeds that of Pt2+ ions by a factor of 37–50. The observation verifies an earlier theoretical prediction and can be understood on the basis of the superatom nature of the spherical cluster. The two main contributions come from ring currents in cluster molecular orbitals hosting the Pt 5d and Pt 6s electrons and from the delocalized hydride shell.

    3. PPI Activators

      You have full text access to this OnlineOpen article
      Identification and X-ray Co-crystal Structure of a Small-Molecule Activator of LFA-1-ICAM-1 Binding (pages 4322–4326)

      Dr. Martin Hintersteiner, Dr. Jörg Kallen, Mario Schmied, Christine Graf, Dr. Thomas Jung, Gemma Mudd, Dr. Steven Shave, Dr. Hubert Gstach and Prof. Manfred Auer

      Version of Record online: 1 APR 2014 | DOI: 10.1002/anie.201310240

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      Tuned up: The LFA-1 ICAM-1 interaction is a fundamental step in T-cell activation in response to antigen encounter. A small-molecule activator of LFA-1, IBE-667, was identified by confocal on-bead screening. The identified activator binds to LFA-1 I domain, as revealed by the co-crystal structure, and increases the affinity of LFA-1 for ICAM-1 on activated T-cells.

    4. Interstitial Clusters

      A Novel Concept for the Synthesis of Multiply Doped Gold Clusters [(M@AunM′m)Lk]q+ (pages 4327–4331)

      Arik Puls, Paul Jerabek, Wataru Kurashige, Moritz Förster, Mariusz Molon, Dr. Timo Bollermann, Manuela Winter, Dr. Christian Gemel, Prof. Dr. Yuichi Negishi, Prof. Dr. Gernot Frenking and Prof. Dr. Roland A. Fischer

      Version of Record online: 2 APR 2014 | DOI: 10.1002/anie.201310436

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      Golden cages: When complexes [M(M′R)a] (M=Mo, Ni, Pd, Pt; M′=Al, Ga; R=CH3, C5Me5; a≥4) react with ClAuPR3 (R=Ph, Me), the interstitial metal atom M (blue) is transferred from the M′a cage (gray) to a Aun shell (yellow). Multiply metal-doped gold clusters [(M@AunM′m)Lk]q+ (n+m≥9; q=0, 1, 3) result. The design rule of the new clusters is based on the 18 valence electron count for the central metal atom M and agrees with the unified superatom concept based on the jellium model.

    5. Natural Product Synthesis

      A Convergent Total Synthesis of the Telomerase Inhibitor (±)-γ-Rubromycin (pages 4332–4336)

      Dr. Michael Wilsdorf and Prof. Dr. Hans-Ulrich Reissig

      Version of Record online: 12 MAR 2014 | DOI: 10.1002/anie.201400315

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      3 building blocks + 3 acids[RIGHTWARDS ARROW]natural product: After the assembly of the crucial precursor from three highly functionalized building blocks, the pivotal spiroketalization was achieved with trifluoromethanesulfonic acid, the isocoumarin formation with fluoroboric acid, and the O-demethylation with the Lewis acid boron tribromide. (±)-γ-Rubromycin was thus synthesized in 18 steps with an overall yield of 3.8 % from commercially available precursors.

    6. Bioorthogonal Reactions

      Protein-Templated Peptide Ligation (pages 4337–4340)

      Nicolas Brauckhoff, Dr. Gernot Hahne, Dr. Johannes T.-H. Yeh and Dr. Tom N. Grossmann

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201400681

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      Come together: A protein template was used to mediate the ligation reaction between two peptides which were equipped with suitable electrophilic and nucleophilic groups. These templated reactions were accelerated by more than three orders of magnitude relative to the nontemplated reactions and proved to be highly selective when used to label proteins within crude cell lysate.

    7. Tetracenes

      Synthesis of Cyano-Substituted Diaryltetracenes from Tetraaryl[3]cumulenes (pages 4341–4345)

      Przemyslaw Gawel, Cagatay Dengiz, Dr. Aaron D. Finke, Dr. Nils Trapp, Prof. Dr. Corinne Boudon, Dr. Jean-Paul Gisselbrecht and Prof. Dr. François Diederich

      Version of Record online: 24 MAR 2014 | DOI: 10.1002/anie.201402299

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      Condensed sensors: The title reaction starts with the cycloaddition of tetracyanoethylenene to the central C[DOUBLE BOND]C bond of cumulenes, followed by a multi-reaction cascade to yield tetracyanodihydrotetracenes. Elimination of (CN)2 provides tetracenes with a rubrene-like substitution pattern as highly fluorescent chromophores that can be used as molecular chemosensors for Cu+ and Ag+ ions.

    8. Ash Dieback

      A Volatile Lactone of Hymenoscyphus pseudoalbidus, Pathogen of European Ash Dieback, Inhibits Host Germination (pages 4346–4349)

      Dr. Christian A. Citron, Dr. Corina Junker, Priv.-Doz. Dr. Barbara Schulz and Priv.-Doz. Dr. Jeroen S. Dickschat

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201402290

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      The largely unknown secondary metabolism of the plant pathogenic fungus Hymenoscyphus pseudoalbidus was investigated by use of the closed-loop stripping apparatus (CLSA) method. A set of volatile lactones was identified by GC/MS. The lactones were synthesized and used in bioassays in which one of the compounds was found to be a strong germination inhibitor for ash seeds.

    9. Enantioselective Gold Catalysis

      A New Type of Chiral Sulfinamide Monophosphine Ligands: Stereodivergent Synthesis and Application in Enantioselective Gold(I)-Catalyzed Cycloaddition Reactions (pages 4350–4354)

      Zhan-Ming Zhang, Peng Chen, Dr. Wenbo Li, Yanfei Niu, Prof. Dr. Xiao-Li Zhao and Prof. Dr. Junliang Zhang

      Version of Record online: 20 MAR 2014 | DOI: 10.1002/anie.201401067

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      Ming-Phos: A new type of simple chiral sulfinamide monophosphine ligands, the so-called Ming-Phos ligands, can be easily prepared from inexpensive and commercially available starting materials. The enantioselectivity of the reaction of yne–enones 1 with nitrones could be controlled by the diastereomeric ligands (R,RS)-M5 and (S,RS)-M5.

    10. Natural Products

      Short Chemoenzymatic Total Synthesis of ent-Hydromorphone: An Oxidative Dearomatization/Intramolecular [4+2] Cycloaddition/Amination Sequence (pages 4355–4358)

      Vimal Varghese and Prof. Tomas Hudlicky

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201400286

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      A short synthesis of ent-hydromorphone has been achieved in twelve steps from β-bromoethylbenzene. The key transformations involved the enzymatic dihydroxylation of the arene to the corresponding cis-dihydrodiol, oxidative dearomatization, subsequent [4+2] cycloaddition to form ring B of the morphinan, and intramolecular amination at C9. Boc=tert-butoxycarbonyl, TBS=tert-butyldimethylsilyl.

    11. Heterogeneous Catalysis

      Convenient and Mild Epoxidation of Alkenes Using Heterogeneous Cobalt Oxide Catalysts (pages 4359–4363)

      Dr. Debasis Banerjee, Dr. Rajenahally V. Jagadeesh, Dr. Kathrin Junge, Dr. Marga-Martina Pohl, Dr. Jörg Radnik, Prof. Dr. Angelika Brückner and Prof. Dr. Matthias Beller

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201310420

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      A general epoxidation of aromatic and aliphatic olefins under mild conditions using recyclable heterogeneous CoxOy–N/C (x=1,3; y=1,4) catalysts and tert-butyl hydroperoxide as the terminal oxidant has been developed. Various stilbenes and aliphatic alkenes were successfully transformed into the corresponding epoxides with high selectivity and good yields.

    12. Reconfigurable Materials

      Selective Janus Particle Assembly at Tipping Points of Thermally-Switched Wetting (pages 4364–4367)

      Changqian Yu, Jie Zhang and Prof. Steve Granick

      Version of Record online: 14 MAR 2014 | DOI: 10.1002/anie.201310465

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      Thermal wetting reversibly joins patchy colloidal particles into clusters and crystals. This is demonstrated with Janus particles made of gold (A) half-coated silica (B) spheres immersed in a mixture of water and 2,6-lutidine such that the relative strength of gold–gold bonding through hydrophobic interaction and silica–silica bonding through wetting-induced attraction is reversibly switched by temperature changes of only 1–2 °C.

    13. Photochemistry

      A Chiral Thioxanthone as an Organocatalyst for Enantioselective [2+2] Photocycloaddition Reactions Induced by Visible Light (pages 4368–4371)

      Dr. Rafael Alonso and Prof. Dr. Thorsten Bach

      Version of Record online: 19 MAR 2014 | DOI: 10.1002/anie.201310997

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      Lighting up S: The thioxanthone 1, which was synthesized in a concise fashion from methyl thiosalicylate, exhibits a significant absorption in the visible-light region. It allows for an efficient enantioselective catalysis of intramolecular [2+2] photocycloaddition reactions, presumably by triplet-energy transfer. Ts=4-toluenesulfonyl.

    14. Hydrogen Evolution Reaction

      Cobalt-Embedded Nitrogen-Rich Carbon Nanotubes Efficiently Catalyze Hydrogen Evolution Reaction at All pH Values (pages 4372–4376)

      Dr. Xiaoxin Zou, Xiaoxi Huang, Dr. Anandarup Goswami, Dr. Rafael Silva, Dr. Bhaskar R. Sathe, Eliška Mikmeková and Prof. Tewodros Asefa

      Version of Record online: 20 MAR 2014 | DOI: 10.1002/anie.201311111

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      The water-splitting reaction still remains far from being practically feasible because of the unavailability of effective catalysts for the hydrogen evolution reaction (HER). A simple synthetic route gives to nitrogen-rich carbon nanotubes that electrocatalyze HER with activities close to that of Pt, and function well under acidic, neutral, or basic media allowing them to be coupled with the best oxygen-evolving catalysts available.

    15. Synthetic Methods

      Dual Platinum and Pyrrolidine Catalysis in the Direct Alkylation of Allylic Alcohols: Selective Synthesis of Monoallylation Products (pages 4377–4381)

      Ryozo Shibuya, Lu Lin, Yasuhito Nakahara, Prof. Dr. Kazushi Mashima and Prof. Dr. Takashi Ohshima

      Version of Record online: 6 MAR 2014 | DOI: 10.1002/anie.201311200

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      Two cats are better than one: The combined use of platinum and pyrrolidine catalysts enabled the direct alkylation of allylic alcohols with reactive methylene compounds. Pyrrolidine was essential for obtaining high selectivity of the monoallylation products, which were produced without the use of excess nucleophiles. cod=1,5-cyclooctadiene, EWG=electron-withdrawing group.

    16. Natural Product Synthesis

      Short Stereoselective Synthesis of the Phytophthora Universal Mating Hormone α1 Using Lithiation/Borylation Reactions (pages 4382–4385)

      Dr. Alexander P. Pulis, Dr. Philipp Fackler and Prof. Varinder K. Aggarwal

      Version of Record online: 14 MAR 2014 | DOI: 10.1002/anie.201400714

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      In search of a mate: The universal mating hormone α 1 of the virulent plant pathogen Phytophthora has been synthesized in 12 steps and 28 % overall yield. Key C[BOND]C bond-forming steps involved the use of two lithiation/borylation reactions to couple together enantioenriched building blocks, one of which also set up the stereochemistry of the tertiary alcohol at C11. The diastereomeric purity of the target molecule is >91 %, the highest obtained to date.

    17. Negishi Reaction Mechanism

      On The Remarkably Different Role of Salt in the Cross-Coupling of Arylzincs From That Seen With Alkylzincs (pages 4386–4389)

      Lucas C. McCann and Prof. Michael G. Organ

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/anie.201400459

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      Pass the salt! Alkyl- and arylzinc halides both require salt (e.g., LiBr, MgCl2) in order to undergo the Negishi cross-coupling reaction—but not for the same reason: Whereas alkylzinc halides must form high-order zincates to undergo transmetallation, in the aryl case the role of the salt is to increase solvent dielectric. Conversely, the analogous diarylzinc much more readily undergoes coupling without salt and in low dielectric solvents.

    18. Amide Synthesis

      Amide Synthesis by Nucleophilic Attack of Vinyl Azides (pages 4390–4394)

      Feng-Lian Zhang, Dr. Yi-Feng Wang, Geoffroy Hervé Lonca, Xu Zhu and Prof. Shunsuke Chiba

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201400938

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      Nitrilium intermediate: A new method for amide synthesis employs vinyl azides as enamine-type nucleophiles towards carbon electrophiles in the presence of BF3⋅OEt2. After nucleophilic attack of the vinyl azide, a substituent of the resulting iminodiazonium ion intermediate A migrates to form nitrilium ion B, which is hydrolyzed to afford the corresponding amide.

    19. Porphyrinoids

      Synthesis of 7,8-Dehydropurpurin Dimers and Their Conversion into Conformationally Constrained β-to-β Vinylene-Bridged Porphyrin Dimers (pages 4395–4398)

      Norihito Fukui, Prof. Dr. Hideki Yorimitsu, Dr. Jong Min Lim, Prof. Dr. Dongho Kim and Prof. Dr. Atsuhiro Osuka

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201400632

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      Bridging the networks: 7,8-Dehydropurpurin dimers were synthesized by twofold Pd-catalyzed [3+2] annulation of meso-bromoporphyrin with 1,4-diphenylbutadiyne. Treatment of this dimer with N-bromosuccinimide (NBS) in CHCl3 and ethanol gave the title porphyrin dimers, which exhibited well-conjugated electronic networks and constrained conformations.

    20. H2S Splitting

      An Integrated Photoelectrochemical–Chemical Loop for Solar-Driven Overall Splitting of Hydrogen Sulfide (pages 4399–4403)

      Dr. Xu Zong, Jingfeng Han, Dr. Brian Seger, Dr. Hongjun Chen, Prof. Gaoqing (Max) Lu, Prof. Dr. Can Li and Prof. Lianzhou Wang

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/anie.201400571

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      Trash to Treasure: A photochemical–chemical loop for the overall H2S splitting was developed by integrating photoelectrochemical H2 production and H2S chemical absorption redox reactions with the link of a redox couple (Fe2+/Fe3+ or I/I3). Using functionalized silicon as photoelectrode, simultaneous extraction of H2 and elemental sulfur from H2S was successfully achieved (see picture).

    21. Sulfination

      Application of Fundamental Organometallic Chemistry to the Development of a Gold-Catalyzed Synthesis of Sulfinate Derivatives (pages 4404–4407)

      Miles W. Johnson, Scott W. Bagley, Prof. Neal P. Mankad, Prof. Robert G. Bergman, Dr. Vincent Mascitti and Prof. F. Dean Toste

      Version of Record online: 20 MAR 2014 | DOI: 10.1002/anie.201400037

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      À la mode: A gold(I)-catalyzed synthesis of sulfinates has been accomplished. Preparation of proposed intermediates, X-ray studies, and a number of mechanistic experiments suggest that an unprecedented mode of reactivity for gold(I) has been achieved. The resulting sulfinates from this reaction can be functionalized in situ to form sulfones and sulfonamides.

    22. Microdroplet Mass Spectrometry

      On-Chip Spyhole Mass Spectrometry for Droplet-Based Microfluidics (pages 4408–4412)

      Natalia Gasilova, Qiuliyang Yu, Dr. Liang Qiao and Prof. Dr. Hubert H. Girault

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201310795

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      Microdroplets are coupled in a simple and efficient manner with electrostatic-spray ionization mass spectrometry using a microchip with a spyhole. Such a set-up allows direct dilution-free droplet ionization with high detection sensitivity. It is suitable for the performance of various single-phase and biphasic reactions, as demonstrated for peptide/protein tryptic digestion and β-lactoglobulin/α-tocopheryl acetate interaction.

    23. Single-Molecule Magnets

      Fine-tuning the Local Symmetry to Attain Record Blocking Temperature and Magnetic Remanence in a Single-Ion Magnet (pages 4413–4417)

      Dr. Liviu Ungur, Jennifer J. Le Roy, Dr. Ilia Korobkov, Prof. Muralee Murugesu and Prof. Liviu F. Chibotaru

      Version of Record online: 20 MAR 2014 | DOI: 10.1002/anie.201310451

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      A record blocking capability of a single-ion magnet has been predicted and obtained. Ab initio calculations on the Er and the isostructural Dy analogue allowed deeper insight into the reasons for the strong magnetic blocking, explaining the striking differences between magnetic behaviors of these two compounds. Dashed line: Calculated orientation of the main magnetic axis in the ground and first excited Kramers doublet.

    24. Polymeric Gels

      Fluorogel Elastomers with Tunable Transparency, Elasticity, Shape-Memory, and Antifouling Properties (pages 4418–4422)

      Dr. Xi Yao, Dr. Stuart S. Dunn, Dr. Philseok Kim, Meredith Duffy, Jack Alvarenga and Prof. Joanna Aizenberg

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201310385

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      Slippery surfaces: Multifunctional fluorogel elastomers with tunable transparency, mechanics, and shape memory properties are reported. After infusing with fluorinated lubricants, the fluorogels demonstrated broad omniphobicity and antifouling against water, hydrocarbon oils, proteins, biological cells, and blood (see picture) while maintaining excellent cytocompatibility.

    25. Solid-State Structures

      Ruthenium(V) Oxides from Low-Temperature Hydrothermal Synthesis (pages 4423–4427)

      Craig I. Hiley, Dr. Martin R. Lees, Dr. Janet M. Fisher, Dr. David Thompsett, Dr. Stefano Agrestini, Dr. Ronald I. Smith and Prof. Richard I. Walton

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201310110

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      Hydrothermal synthesis yields the ruthenium(V)-containing oxides Ca1.5Ru2O7 , SrRu2O6 , and Ba2Ru3O9(OH). These oxides show a range of structures and magnetic properties. SrRu2O6 is a hexagonal layered oxide that exhibits antiferromagnetic ordering to at least 230 °C, whilst the orthorhombic Ba2Ru3O9(OH) is a ferromagnetic oxyhydroxide. All three ruthenates are metastable and readily collapse to other oxides at 300–500 °C.

    26. Enzymatic Deracemization

      Tailoring D-Amino Acid Oxidase from the Pig Kidney to R-Stereoselective Amine Oxidase and its Use in the Deracemization of α-Methylbenzylamine (pages 4428–4431)

      Kazuyuki Yasukawa, Dr. Shogo Nakano and Prof. Dr. Yasuhisa Asano

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201308812

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      A change in selectivity: An engineered porcine kidney D-amino acid oxidase (pkDAO) with markedly changed substrate selectivity towards R amines was obtained by directed evolution. The mutant enzyme exhibited a high preference towards the substrate α-methylbenzylamine and was used to synthesize the S-configured amine through deracemization.

    27. Asymmetric Catalysis

      Axially Chiral Imidodiphosphoric Acid Catalyst for Asymmetric Sulfoxidation Reaction: Insights on Asymmetric Induction (pages 4432–4436)

      Garima Jindal and Prof. Raghavan B. Sunoj

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201309532

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      Turn the stereo up: The first transition-state (TS) model for a new class of axially chiral imidodiphosphoric acid catalysts in the title reaction is proposed using DFT(M06-2X) calculations. The recognition of the substrate in the chiral pocket and a series of weak noncovalent interactions are responsible for stereoinduction. This stereoelectronic model differs from the commonly employed models which rely on steric interactions.

    28. MOF Memristor

      Storage of Electrical Information in Metal–Organic-Framework Memristors (pages 4437–4441)

      Dr. Seok Min Yoon, Dr. Scott C. Warren and Prof. Bartosz A. Grzybowski

      Version of Record online: 14 MAR 2014 | DOI: 10.1002/anie.201309642

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      Memories are forever: The sub-nanometer pore size that exists in a metal–organic framework allows electrical information to be written, read, and re-written when that MOF is infiltrated with an ionic electrolyte.

    29. Self-Assembly

      Gated Electron Sharing Within Dynamic Naphthalene Diimide-Based Oligorotaxanes (pages 4442–4449)

      Alyssa-Jennifer Avestro, Daniel M. Gardner, Dr. Nicolaas A. Vermeulen, Eleanor A. Wilson, Dr. Severin T. Schneebeli, Dr. Adam C. Whalley, Dr. Matthew E. Belowich, Prof. Raanan Carmieli, Prof. Michael R. Wasielewski and Prof. J. Fraser Stoddart

      Version of Record online: 12 MAR 2014 | DOI: 10.1002/anie.201309680

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      Birds of a feather flock together: Mutually π-stacked small-molecule naphthalene diimide (NDI) [24]crown-8 derivatives self-assemble dynamically on a repeating –(CH2CH2NH2+CH2)–template to afford the stepwise evolution of discrete-length oligorotaxanes, which are shown to communicate electronically through their co-facially interacting π-surfaces, sharing electrons across linear arrays containing one, two, three, and four NDI units as determined by cyclic voltammetry and EPR/ENDOR spectroscopies.

    30. Helical Structures

      Lamellar-Twisting-Induced Circular Dichroism of Chromophore Moieties in Banded Spherulites with Evolution of Homochirality (pages 4450–4455)

      Dr. Ming-Chia Li, Hsiao-Fang Wang, Chen-Hung Chiang, Prof. Yu-Der Lee and Prof. Rong-Ming Ho

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201310078

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      Supramolecular chirality: By evolution of homochirality from helical polymer chains (conformational chirality) to twisting lamellae (hierarchical chirality), banded spherulites with preferential handedness are formed by crystallization of chiral polymers end-capped with chromophore through cooperative intramolecular and intermolecular interactions, changing the chromophore moiety from “optically inactive” to “optically active”.

    31. Gold Catalysis

      A Highly Efficient and Broadly Applicable Cationic Gold Catalyst (pages 4456–4459)

      Deepika Malhotra, Mark S. Mashuta, Prof. Dr. Gerald B. Hammond and Prof. Dr. Bo Xu

      Version of Record online: 20 MAR 2014 | DOI: 10.1002/anie.201310239

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      Less is better: A broadly applicable cationic gold catalyst was developed that works at extremely low loading and relatively low temperature. The new gold catalyst containing a bis(biphenyl) phosphane ligand was tested in many common types of gold-catalyzed reactions including intra- and intermolecular X[BOND]H (X=C, N, O) additions to alkynes (see example) and cycloisomerizations of enyne and allenone.

    32. Lithium-Ion Batteries

      In Situ Three-Dimensional Synchrotron X-Ray Nanotomography of the (De)lithiation Processes in Tin Anodes (pages 4460–4464)

      Dr. Jiajun Wang, Dr. Yu-chen Karen Chen-Wiegart and Dr. Jun Wang

      Version of Record online: 19 MAR 2014 | DOI: 10.1002/anie.201310402

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      Microstructural evolution: In situ synchrotron X-ray nanotomography has been developed to track the microstructural evolution of battery materials during the cycling of a battery. This three-dimensional quantitative analysis and visualization on the nanometer scale should contribute to our understanding of energy materials and lead to improvements of their synthetic processing.

    33. Photo-annealing

      A Photo-annealing Approach for Building Functional Polymer Layers on Paper (pages 4465–4468)

      Qiuping Qian, Jian Wang, Prof. Feng Yan and Prof. Yapei Wang

      Version of Record online: 12 MAR 2014 | DOI: 10.1002/anie.201310714

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      Red hot: A photo-annealing approach was developed for building functional polymer layers on paper. Conducting polyaniline that can undergo photothermal conversion can be readily annealed by near-infrared light. The porous structure is retained in the annealed polymer but it becomes insulating and hydrophobic. Selective photo-annealing produces a functional layer with patterned conductive arrays, which exhibits real-time response to ammonia gas.

    34. Drug Delivery

      An Activatable Theranostic for Targeted Cancer Therapy and Imaging (pages 4469–4474)

      Dr. Sankarprasad Bhuniya, Dr. Sukhendu Maiti, Dr. Eun-Joong Kim, Hyunseung Lee, Prof. Jonathan L. Sessler, Dr. Kwan Soo Hong and Prof. Jong Seung Kim

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201311133

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      All in one: A new theranostic prodrug was developed containing a biotinylated piperazine-rhodol conjugate linked to the drug SN-38 through a self-immolative disulfide spacer. When exposed to cellular thiols in cancer cells, it is able to release the active chemotherapeutic, SN38, along with a diagnostic fluorophore. This theranostic framework permits the targeted delivery, release of an active agent (SN-38), and its facile monitoring in vitro and in vivo.

    35. NMR Spectroscopy

      Next-Generation Heteronuclear Decoupling for High-Field Biomolecular NMR Spectroscopy (pages 4475–4479)

      Dr. Franz Schilling, Dr. Lisa R. Warner, Dr. Naum I. Gershenzon, Prof. Dr. Thomas E. Skinner, Prof. Dr. Michael Sattler and Prof. Dr. Steffen J. Glaser

      Version of Record online: 12 MAR 2014 | DOI: 10.1002/anie.201400178

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      Availability of ultra-high magnetic fields in NMR spectroscopy requires increased bandwidth for heteronuclear decoupling. While composite pulse decoupling is limited in the achievable bandwidth, adiabatic pulse decoupling is compromised by sideband artifacts. A novel low-power decoupling pulse that achieves broadband uniform sideband suppression (BUSS) is reported.

    36. Electroactive Biofilms

      Highly Active Bidirectional Electron Transfer by a Self-Assembled Electroactive Reduced-Graphene-Oxide-Hybridized Biofilm (pages 4480–4483)

      Prof. Yang-Chun Yong, Yang-Yang Yu, Prof. Xinhai Zhang and Prof. Hao Song

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201400463

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      Shocking bacteria! The title biofilm was constructed by the one-step in situ bioreduction and self-assembly of graphene oxide (GO) with Shewanella oneidensis. The resulting 3D macroporous rGO/bacteria hybrid biofilm gave a 25-fold increase in maximum oxidation current in microbial fuel cells, and a 74-fold increase in reduction current in microbial electrosynthesis over that of the naturally occurring biofilms.

    37. Metal Phosphinidenes

      You have full text access to this OnlineOpen article
      Triamidoamine–Uranium(IV)-Stabilized Terminal Parent Phosphide and Phosphinidene Complexes (pages 4484–4488)

      Dr. Benedict M. Gardner, Dr. Gábor Balázs, Prof. Dr. Manfred Scheer, Dr. Floriana Tuna, Prof. Eric J. L. McInnes, Dr. Jonathan McMaster, Dr. William Lewis, Prof. Alexander J. Blake and Prof. Stephen T. Liddle

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/anie.201400798

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      Straightforward deprotonation of the first f-block terminal parent phosphide complex and potassium abstraction results in the isolation of an unprecedented structurally authenticated metal-stabilized terminal parent phosphinidene complex. B15C5=benzo-15-crown-5 ether.

    38. N-Heterocyclic Carbenes

      Fusing N-Heterocyclic Carbenes with Carborane Anions (pages 4489–4493)

      Dr. Ahmad El-Hellani and Prof. Vincent Lavallo

      Version of Record online: 24 MAR 2014 | DOI: 10.1002/anie.201402445

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      Three in one: A novel family of polyanionic N-heterocyclic carbene–lithium adducts are reported, that feature two N-bonded weakly coordinating carborane anions. Judicious choice of base allows the selective deprotonation of an anionic imidazolium to form either a normal C2 or an abnormal C5 imidazolylidene. When treated with nBuLi the monoanionic imidazolium produces a doubly deprotonated trianionic C2,C5 dilithium complex.

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