Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 41

October 6, 2014

Volume 53, Issue 41

Pages 10829–11095

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Obituary
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    1. You have free access to this content
      Cover Picture: Mononuclear and Terminal Zirconium and Hafnium Methylidenes (Angew. Chem. Int. Ed. 41/2014) (page 10829)

      Dr. Masahiro Kamitani, Balazs Pinter, Dr. Chun-Hsing Chen, Dr. Maren Pink and Prof. Dr. Daniel J. Mindiola

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201408379

      Thumbnail image of graphical abstract

      Kinetically stable methylidene complexes of zirconium and hafnium were prepared through photolysis-induced α-H abstraction from the corresponding complexes with aryloxide and two methyl ligands. In their Communication on page 10913 ff., D. J. Mindiola and co-workers describe their quest for a kinetically more resistant system (structure on top of the compass) by taking advantage of prior systems (old map with drawings), thus finding the target molecule (inside the treasure chest).

    2. You have free access to this content
      Inside Cover: Interconvertible Living Radical and Cationic Polymerization through Reversible Activation of Dormant Species with Dual Activity (Angew. Chem. Int. Ed. 41/2014) (page 10830)

      Dr. Hiroshi Aoshima, Mineto Uchiyama, Prof. Dr. Kotaro Satoh and Prof. Dr. Masami Kamigaito

      Article first published online: 14 AUG 2014 | DOI: 10.1002/anie.201407932

      Thumbnail image of graphical abstract

      Two monomers can be copolymerized by a new method via different intermediates into a single polymer chain. In their Communication on page 10932 ff., K. Satoh, M. Kamigaito, and co-workers present interconvertable radical and cationic copolymerization of vinyl ether and acrylate by dual reversible activation of dormant thioesters with a radical species and a Lewis acid. A controlled multiblock copolymer comprising radically and cationically polymerized segments could be prepared.

    3. You have free access to this content
      Inside Back Cover: Molecular Salt Effects in the Gas Phase: Tuning the Kinetic Basicity of [HCCLiCl] and [HCCMgCl2] by LiCl and MgCl2 (Angew. Chem. Int. Ed. 41/2014) (page 11097)

      Dr. George N. Khairallah, Dr. Gabriel da Silva and Prof. Richard A. J. O'Hair

      Article first published online: 14 AUG 2014 | DOI: 10.1002/anie.201408030

      Thumbnail image of graphical abstract

      The mystery of why water and salt contaminants destroy organometallic reagents has been solved by G. N. Khairallah, G. da Silva, and R. A. J. O'Hair in their Communication on page 10979 ff. The addition of an individual salt molecule to an organometallic reagent dramatically enhances its reactivity towards water. This second metal center plays an active role in altering the fundamental chemical transformations that take place when water attacks the organometallic compound.

    4. You have free access to this content
      Back Cover: Harvesting Solar Light with Crystalline Carbon Nitrides for Efficient Photocatalytic Hydrogen Evolution (Angew. Chem. Int. Ed. 41/2014) (page 11098)

      Dr. Manas K. Bhunia, Dr. Kazuo Yamauchi and Prof. Kazuhiro Takanabe

      Article first published online: 19 AUG 2014 | DOI: 10.1002/anie.201407927

      Thumbnail image of graphical abstract

      Metal-free photocatalysts for visible-light-driven H2 evolution that are inexpensive are coveted for energy production. K. Takanabe and co-workers show in their Communication on page 11001 ff. that a family of crystalline carbon nitrides (CNs) obtained by supramolecular aggregation and ionic melt polycondensation gives excellent photocatalytic H2 evolution. Controlling the amount and arrangements of dopants in the CN structure enables a substantial amount of visible light to be harvested and enhances the photocatalytic performance.

  2. Frontispiece

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Obituary
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    1. You have free access to this content
      Frontispiece: Re-Appearance of Cooperativity in Ultra-Small Spin-Crossover [Fe(pz){Ni(CN)4}] Nanoparticles

      Haonan Peng, Dr. Simon Tricard, Gautier Félix, Dr. Gábor Molnár, Dr. William Nicolazzi, Dr. Lionel Salmon and Dr. Azzedine Bousseksou

      Article first published online: 29 SEP 2014 | DOI: 10.1002/anie.201484171

      Thumbnail image of graphical abstract

      Spin-Crossover Nanoparticles

  3. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Obituary
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    1. Graphical Abstract: Angew. Chem. Int. Ed. 41/2014 (pages 10833–10847)

      Article first published online: 29 SEP 2014 | DOI: 10.1002/anie.201490039

  4. Corrigendum

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

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Obituary
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    1. Patrick J. Walsh (page 10854)

      Article first published online: 18 JUN 2014 | DOI: 10.1002/anie.201405235

      Thumbnail image of graphical abstract

      “The most exciting thing about my research is my research team is highly motivated, passionate about science, and rapidly generates interesting results. My biggest motivation is the thrill of doing more innovative science than we did last week …” This and more about Patrick J. Walsh can be found on page 10854.

  7. News

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

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Obituary
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    1. Sheldon Shore (1930–2014) (page 10856)

      Prof. Dr. Malcolm H. Chisholm

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201408000

      Thumbnail image of graphical abstract
  9. Book Review

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Obituary
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    1. Around the World in 18 Elements. By David Scott. (page 10857)

      Andreas Grohmann

      Article first published online: 29 SEP 2014 | DOI: 10.1002/anie.201407478

      Thumbnail image of graphical abstract

      Royal Society of Chemistry, Cambridge, 2014. 235 pp., softcover, £ 19.99.—ISBN 978-1849738040

  10. Highlights

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

      A Step Closer to the Electrochemical Production of Liquid Fuels (pages 10858–10860)

      Dr. Klaas Jan P. Schouten, Dr. Federico Calle-Vallejo and Prof. Dr. Marc T. M. Koper

      Article first published online: 31 JUL 2014 | DOI: 10.1002/anie.201406174

      Thumbnail image of graphical abstract

      Fueled by success: A nanostructured copper electrocatalyst derived from copper oxide can reduce carbon monoxide to multicarbon oxygenates, including ethanol. This is an important step in the production of liquid fuel by the reduction of CO2 using electricity from renewable sources.

    2. Arenes

      Organocatalytic Enantioselective Construction of Polyaromatic Architectures (pages 10861–10863)

      Ophélie Quinonero, Dr. Cyril Bressy and Dr. Xavier Bugaut

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406263

      Thumbnail image of graphical abstract

      Aromatics in 3D: Organocatalysis is now reaching beyond the control of stereogenic centers and opens new possibilities for the construction of complex polyaromatic structures with either helical or axial chirality.

    3. Proteomics

      From the Human Genome to the Human Proteome (pages 10864–10866)

      Dr. Javier Muñoz and Prof. Dr. Albert J. R. Heck

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201406545

      Thumbnail image of graphical abstract

      A herculean task: Determining the human proteome sets the ultimate challenge in cell biology as it is thought to consist of more than 1 000 000 proteoforms, in contrast to “only” 20 000 protein-coding genes. Two teams of researchers have now proved the translation of 18 000 proteins (and more than 27 000 isoforms) by mass spectrometry. They obtained important information on the extent of protein translation and alternative splicing.

  11. Minireview

    1. Top of page
    2. Cover Pictures
    3. Frontispiece
    4. Graphical Abstract
    5. Corrigendum
    6. News
    7. Author Profile
    8. News
    9. Obituary
    10. Book Review
    11. Highlights
    12. Minireview
    13. Review
    14. Communications
    1. Chiral-at-Metal Complexes

      Asymmetric Catalysis Mediated by the Ligand Sphere of Octahedral Chiral-at-Metal Complexes (pages 10868–10874)

      Dr. Lei Gong, B.Sc. Liang-An Chen and Prof. Dr. Eric Meggers

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201404305

      Thumbnail image of graphical abstract

      “Organocatalysis” with metal complexes: Inert octahedral metal complexes are an emerging class of catalysts for asymmetric synthesis. In these compounds the globular, rigid nature and stereochemical options of octahedral compounds are exploited. Complexes like those shown promise new opportunities in the field of catalysis.

  12. Review

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

      Enzymatic Degradation of (Ligno)cellulose (pages 10876–10893)

      Prof. Dr. Uwe Bornscheuer, Prof. Dr. Klaus Buchholz and Prof. Dr. Jürgen Seibel

      Article first published online: 18 AUG 2014 | DOI: 10.1002/anie.201309953

      Thumbnail image of graphical abstract

      A stubborn raw material: The conversion of cellulosic biomass into low-price biofuels and high-value-added chemicals is a very challenging goal. This Review addresses the development of the enzymatic catalytic degradation of (ligno)cellulose (see picture), including achievements in the areas of chemical-reaction engineering, structural biochemistry, and catalyst design.

  13. Communications

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

      Re-Appearance of Cooperativity in Ultra-Small Spin-Crossover [Fe(pz){Ni(CN)4}] Nanoparticles (pages 10894–10898)

      Haonan Peng, Dr. Simon Tricard, Gautier Félix, Dr. Gábor Molnár, Dr. William Nicolazzi, Dr. Lionel Salmon and Dr. Azzedine Bousseksou

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406710

      Thumbnail image of graphical abstract

      Spin-crossover nanoparticles: Mössbauer spectroscopy was used to determine the variation of the Debye temperature (θD) for [Fe(pz){Ni(CN)4}] (py=pyrazine) spin-crossover nanoparticles ranging from 2 to 110 nm (see picture). The investigations explain the re-appearance of cooperativity in the smallest nanoparticles.

    2. Dendrimers

      Mimicking Biological Membranes with Programmable Glycan Ligands Self-Assembled from Amphiphilic Janus Glycodendrimers (pages 10899–10903)

      Dr. Shaodong Zhang, Dr. Ralph-Olivier Moussodia, Dr. Hao-Jan Sun, Dr. Pawaret Leowanawat, Adam Muncan, Christopher D. Nusbaum, Kathleen M. Chelling, Prof. Dr. Paul A. Heiney, Prof. Dr. Michael L. Klein, Priv.-Doz. Dr. Sabine André, Prof. Dr. René Roy, Prof. Dr. Hans-J. Gabius and Prof. Dr. Virgil Percec

      Article first published online: 12 JUN 2014 | DOI: 10.1002/anie.201403186

      Thumbnail image of graphical abstract

      Glycodendrimersomes: Amphiphilic Janus glycodendrimers with different topologies self-assemble into uniform unilamellar soft vesicles, denoted glycodendrimersomes, which are stable over time. They exhibit specific and potent bioactivity in binding biomedically relevant lectins. The vesicles with multivalent glycan ligands extending beyond their surface were shown to provide optimal glycan ligand display.

    3. Protein Design

      Optogenetic Engineering: Light-Directed Cell Motility (pages 10904–10907)

      Prof. Dr. Robert M. Hughes and Prof. Dr. David S. Lawrence

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201404198

      Thumbnail image of graphical abstract

      Shine a light: A straightforward strategy for the acquisition of genetically encoded, light-activatable proteins is based upon the principles set forth in the 100 year old Michaelis–Menten Equation. Photoactivation of a light-responsive cofilin mediates cytoskeleton remodelling, lamellipodia and filopodia formation, and directed cell motility.

    4. Luminescence

      A Phosphorescent Molecular “Butterfly” that undergoes a Photoinduced Structural Change allowing Temperature Sensing and White Emission (pages 10908–10912)

      Dr. Mingu Han, Yu Tian, Dr. Zhao Yuan, Prof. Lei Zhu and Prof. Biwu Ma

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201405293

      Thumbnail image of graphical abstract

      The white brothers: A molecular “butterfly”, that is, a phosphorescent PtII binuclear complex, can flap its “wings” and generate dual (white) emission upon photoexcitation. This photoinduced molecular structure change results from the shortening of the Pt–Pt distance in the excited state and is phase-dependent allowing application of the complex as a self-referenced luminescent sensor for phase change, temperature, and viscosity.

    5. Methylidene Complexes | Hot Paper

      Mononuclear and Terminal Zirconium and Hafnium Methylidenes (pages 10913–10915)

      Dr. Masahiro Kamitani, Balazs Pinter, Dr. Chun-Hsing Chen, Dr. Maren Pink and Prof. Dr. Daniel J. Mindiola

      Article first published online: 11 AUG 2014 | DOI: 10.1002/anie.201405042

      Thumbnail image of graphical abstract

      The photolysis of zirconium or hafnium complexes with one aryloxide and two methyl ligands induces α-hydrogen abstraction and results in the formation of mononuclear complexes with terminal methylidene ligands. These unique systems have been fully characterized, including the determination of the solid-state structure in the case of the zirconium complex.

    6. Analytical Methods

      Lysosomal pH Rise during Heat Shock Monitored by a Lysosome-Targeting Near-Infrared Ratiometric Fluorescent Probe (pages 10916–10920)

      Dr. Qiongqiong Wan, Prof. Dr. Suming Chen, Prof. Dr. Wen Shi, Lihong Li and Prof. Dr. Huimin Ma

      Article first published online: 22 AUG 2014 | DOI: 10.1002/anie.201405742

      Thumbnail image of graphical abstract

      Feeling hot, hot, hot: A near-infrared ratiometric pH probe with a stable semicyanine skeleton has been developed for lysosomal pH measurements. The readily preparable probe shows an excellent lysosome-targeting ability and high photostability. The probe has been used to investigate the change of lysosomal pH with temperature, revealing for the first time that lysosomal pH values rise during heat shock and the process is irreversible.

    7. Bioorthogonal Chemistry | Hot Paper

      Super-Resolution Imaging of Plasma Membrane Glycans (pages 10921–10924)

      Sebastian Letschert, Dr. Antonia Göhler, Christian Franke, Nadja Bertleff-Zieschang, Elisabeth Memmel, Priv.-Doz. Dr. Sören Doose, Prof. Dr. Jürgen Seibel and Prof. Dr. Markus Sauer

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406045

      Thumbnail image of graphical abstract

      Glycan spotting: Click chemistry and super-resolution imaging was used to visualize and quantify ManNAc-, GalNAc-, and O-GlcNAc-modified glycans in the plasma membrane of mammalian cells with single-molecule sensitivity (see image). The data demonstrate that a single cell may easily contain more than ten million glycans, which are homogeneously distributed and do not form clusters or nanodomains.

    8. Biocatalysis

      You have full text access to this OnlineOpen article
      Oxygenase-Catalyzed Desymmetrization of N,N-Dialkyl-piperidine-4-carboxylic Acids (pages 10925–10927)

      Anna M. Rydzik, Ivanhoe K. H. Leung, Grazyna T. Kochan, Michael A. McDonough, Timothy D. W. Claridge and Prof. Christopher J. Schofield

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406125

      Thumbnail image of graphical abstract

      Thinking outside the BBOX: γ-Butyrobetaine hydroxylase (BBOX) is a 2-oxoglutarate (2OG) dependent oxygenase that catalyzes the final hydroxylation step in the biosynthesis of carnitine. BBOX was shown to catalyze the oxidative desymmetrization of achiral N,N-dialkyl-piperidine-4-carboxylates to give products with two or three stereogenic centers.

    9. Bioconjugation | Hot Paper

      Dialdehydes Lead to Exceptionally Fast Bioconjugations at Neutral pH by Virtue of a Cyclic Intermediate (pages 10928–10931)

      Pascal Schmidt, Dr. Linna Zhou, Kiril Tishinov, Kaspar Zimmermann and Prof. Dr. Dennis Gillingham

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406132

      Thumbnail image of graphical abstract

      For aldehydes, 1+1=500: Dialdehydes react with O-alkylhydroxylamines at rates of 500 M−1 s−1 at neutral pH values in the absence of catalysts. The key to these conjugations is an unusually stable cyclic intermediate, which ultimately undergoes dehydration to yield an oxime. The application of this method in bioconjugations and a mechanistic interpretation are outlined.

    10. Copolymerization

      Interconvertible Living Radical and Cationic Polymerization through Reversible Activation of Dormant Species with Dual Activity (pages 10932–10936)

      Dr. Hiroshi Aoshima, Mineto Uchiyama, Prof. Dr. Kotaro Satoh and Prof. Dr. Masami Kamigaito

      Article first published online: 11 AUG 2014 | DOI: 10.1002/anie.201406590

      Thumbnail image of graphical abstract

      Dr. Jekyll and Mr. Hyde: A dormant thioester bond with dual activity is reversibly activated by radicals and Lewis acids to induce concurrent radical and cationic polymerizations. This method enables the controlled synthesis of multiblock copolymers comprised of different types of segments that cannot be prepared with a single intermediate.

    11. Collective Tunneling | Very Important Paper

      Exceptional Isotopic-Substitution Effect: Breakdown of Collective Proton Tunneling in Hexagonal Ice due to Partial Deuteration (pages 10937–10940)

      Dr. Christof Drechsel-Grau and Prof. Dr. Dominik Marx

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201405989

      Thumbnail image of graphical abstract

      Ab initio simulations clarify the effects of H/D isotopic substitution on the mechanism of the collective tunneling of six protons within proton-ordered cyclic water hexamers that are contained in proton-disordered ice. At the transition state, isotopic substitution leads to a Zundel-like [HO⋅⋅⋅D⋅⋅⋅OH] complex with localized ionic defects and thus inhibits perfectly correlated proton tunneling.

    12. Conformational Space

      Exploration of Conformational Spaces of High-Mannose-Type Oligosaccharides by an NMR-Validated Simulation (pages 10941–10944)

      Dr. Takumi Yamaguchi, Dr. Yoshitake Sakae, Dr. Ying Zhang, Sayoko Yamamoto, Prof. Yuko Okamoto and Prof. Koichi Kato

      Article first published online: 4 SEP 2014 | DOI: 10.1002/anie.201406145

      Thumbnail image of graphical abstract

      Watch this space: Lanthanide- and isotope-assisted NMR approaches combined with replica-exchange molecular dynamics simulations have been used to describe the conformational dynamics of complicated, branched oligosaccharides. The experimentally validated simulation provided quantitative views of the dynamic conformational ensembles of oligosaccharides with triantennary structures.

    13. Drug Delivery

      Cell-Mediated Assembly of Phototherapeutics (pages 10945–10948)

      Weston J. Smith, Nathan P. Oien, Dr. Robert M. Hughes, Christina M. Marvin, Zachary L. Rodgers, Junghyun Lee and Prof. David S. Lawrence

      Article first published online: 22 AUG 2014 | DOI: 10.1002/anie.201406216

      Thumbnail image of graphical abstract

      Window of opportunity: A wavelength-encoded drug-delivery strategy operates within the optical window of tissue. The photoresponsive system is acquired by the assembly of lipid-cobalamin-drug and lipid-fluorophore constructs on the surface of erythrocytes. The desired wavelength of cobalamin-drug photocleavage is “dialed-in” by simply choosing the appropriate lipid-fluorophore “antenna”.

    14. Controlled Drug Delivery

      Molecularly Precise Dendrimer–Drug Conjugates with Tunable Drug Release for Cancer Therapy (pages 10949–10955)

      Dr. Zhuxian Zhou, Dr. Xinpeng Ma, Dr. Caitlin J. Murphy, Dr. Erlei Jin, Dr. Qihang Sun, Prof. Youqing Shen, Edward A. Van Kirk and Prof. William J. Murdoch

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406442

      Thumbnail image of graphical abstract

      Camptothecine core: Polylysine dendrimers with the conjugated drug in the core were synthesized for cancer therapy. The release rates of the camptothecine conjugates were easily tunable by adjusting the dendrimer generation and the peripheral functional groups as well as the pH. Conjugates showing a fast drug release also exhibited a high anticancer activity against intraperitoneal and subcutaneous tumors.

    15. RNA Targeting

      A Toxic RNA Catalyzes the In Cellulo Synthesis of Its Own Inhibitor (pages 10956–10959)

      Dr. Suzanne G. Rzuczek, Dr. HaJeung Park and Prof. Dr. Matthew D. Disney

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406465

      Thumbnail image of graphical abstract

      Potent modulators of RNA function can be assembled in cellulo by using the cell as the reaction vessel and a disease-causing RNA as the catalyst. In particular, a Huisgen 1,3-dipolar cycloaddition reaction was used to template the synthesis of an RNA inhibitor in disease-affected cells.

    16. Oxygen Evolution

      You have full text access to this OnlineOpen article
      Water-Splitting Electrocatalysis in Acid Conditions Using Ruthenate-Iridate Pyrochlores (pages 10960–10964)

      Dr. Kripasindhu Sardar, Enrico Petrucco, Craig I. Hiley, Dr. Jonathan D. B. Sharman, Dr. Peter P. Wells, Prof. Andrea E. Russell, Dr. Reza J. Kashtiban, Dr. Jeremy Sloan and Prof. Richard I. Walton

      Article first published online: 4 SEP 2014 | DOI: 10.1002/anie.201406668

      Thumbnail image of graphical abstract

      Ru/Ir cooperativity: A pyrochlore solid solution (Na0.33Ce0.67)2(Ir1−xRux)2O7 formed as nanocrystalline powder under hydrothermal conditions shows high activity for electrochemical oxygen evolution in aqueous acid. In situ XAFS experiments show a cooperative effect of Ru and Ir that depends on the composition of the material. OER=oxygen evolution reaction.

    17. Metal–Organic Supercontainers

      pH-Modulated Molecular Assemblies and Surface Properties of Metal–Organic Supercontainers at the Air–Water Interface (pages 10965–10969)

      Nathan L. Netzer, Dr. Feng-Rong Dai, Prof. Zhenqiang Wang and Prof. Chaoyang Jiang

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406733

      Thumbnail image of graphical abstract

      MOSC thin films: The molecular assemblies of metal–organic supercontainers (MOSCs) were studied at the air–water interface. Variation in the pH values of the subphases causes significant changes in the molecular orientation in the Langmuir films. The uniform MOSC structures in Langmuir–Blodgett films show tunable surface properties that can be precisely controlled by the fabricating conditions.

    18. Natural Products

      Total Synthesis of Myceliothermophins C, D, and E (pages 10970–10974)

      Prof. Dr. K. C. Nicolaou, Dr. Lei Shi, Dr. Min Lu, Dr. Manas R. Pattanayak, Dr. Akshay A. Shah, Dr. Heraklidia A. Ioannidou and Dr. Manjunath Lamani

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406815

      Thumbnail image of graphical abstract

      Cascades: The total synthesis of the cytotoxic myceliothermophins C, D, and E have been achieved through a sequence involving a cascade bis(cyclization) of epoxide or aldehyde substrates to forge a trans-fused decalin precursor of the natural products.

    19. Receptor Targeting

      A Multivalent Ligand for the Mannose-6-Phosphate Receptor for Endolysosomal Targeting of an Activity-Based Probe (pages 10975–10978)

      Dr. Sascha Hoogendoorn, Dr. Gijs H. M. van Puijvelde, Prof. Dr. Johan Kuiper, Prof. Dr. Gijs A. van der Marel and Prof. Dr. Herman S. Overkleeft

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406842

      Thumbnail image of graphical abstract

      On target: A synthetic glycopeptide (P) that contains six mannose-6-phosphate residues was covalently attached to a fluorescent activity-based probe for cathepsins. The construct was internalized in live cells through binding to the mannose-6-phosphate receptor (MPR), thus validating the cluster as an MPR-targeting ligand that can be used to deliver cargo into the endolysosomal pathway.

    20. Gas-Phase Reactions

      Molecular Salt Effects in the Gas Phase: Tuning the Kinetic Basicity of [HCCLiCl] and [HCCMgCl2] by LiCl and MgCl2 (pages 10979–10983)

      Dr. George N. Khairallah, Dr. Gabriel da Silva and Prof. Richard A. J. O'Hair

      Article first published online: 30 JUL 2014 | DOI: 10.1002/anie.201404362

      Thumbnail image of graphical abstract

      How do individual salt molecules influence the kinetic basicity of organometallates reacting with water? Addition of LiCl to [HCCLiCl] or [HCCMgCl2] enhances their reactivity towards water by a factor of about two, while addition of MgCl2 to [HCCMgCl2] enhances its reactivity by a factor of about four (see picture). The mechanism of hydration has been studied theoretically.

    21. Radicals

      An Amphoteric Switch to Aromatic and Antiaromatic States of a Neutral Air-Stable 25π Radical (pages 10984–10987)

      Tullimilli Y. Gopalakrishna, Dr. J. Sreedhar Reddy and Prof. Dr. Venkataramanarao G. Anand

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201406893

      Thumbnail image of graphical abstract

      Super stable: A 25π radical of an expanded isophlorin undergoes reversible one-electron oxidation to form 24π antiaromatic species and one-electron reduction to form 26π aromatic species, confirming its amphoteric behavior. All of the three oxidation states of the macrocycle have been characterized in solution and the solid state to confirm their stability under ambient conditions.

    22. Flavin Redox Bifurcation

      Flavin Redox Bifurcation as a Mechanism for Controlling the Direction of Electron Flow during Extracellular Electron Transfer (pages 10988–10991)

      Dr. Akihiro Okamoto, Prof. Dr. Kazuhito Hashimoto and Prof. Dr. Kenneth H. Nealson

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201407004

      Thumbnail image of graphical abstract

      The iron-reducing bacterium­ Shewanella oneidensis MR-1 has a dual directional electronic conduit involving 40 heme redox centers in flavin-binding outer-membrane c-type cytochromes (OM c-Cyts). The redox bifurcation of the cell-secreted riboflavin cofactor in OM c-Cyts switches the direction of electron conduction in the biological conduit at the cell–electrode interface to drive either bacterial electrode reduction or oxidation reactions. Sq=semiquinone, Hq=hydroquinone.

    23. Synthetic Methods | Very Important Paper

      Highly Diastereoselective and Enantiospecific Allylation of Ketones and Imines Using Borinic Esters: Contiguous Quaternary Stereogenic Centers (pages 10992–10996)

      Dr. Jack L.-Y. Chen and Prof. Dr. Varinder K. Aggarwal

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201407127

      Thumbnail image of graphical abstract

      Goldilocks reactivity: 3,3-Disubstituted allylic borinic esters possess the perfect balance between reactivity and configurational stability to react with both ketones and ketimines, allowing facile access to adjacent quaternary stereocenters with full stereocontrol. Synthesis of all possible stereoisomers of a quaternary-quaternary motif is demonstrated. TFAA=trifluoroacetic anhydride.

    24. Synthetic Methods

      An Unusual Ring-Contraction/Rearrangement Sequence for Making Functionalized Di- and Triquinanes (pages 10997–11000)

      Chinta Nagaraju and Prof. Dr. Kavirayani R. Prasad

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201407680

      Thumbnail image of graphical abstract

      In sync: An unusual rearrangement involving a ring contraction and subsequent intramolecular trapping of the incipient oxocarbenium ion with an alkene has been observed. The rearrangement offers a new route to structurally complex diquinanes (see scheme). The sequence was extended to the synthesis of an oxymethano-bridged triquinane framework.

    25. Photocatalysis | Hot Paper

      Harvesting Solar Light with Crystalline Carbon Nitrides for Efficient Photocatalytic Hydrogen Evolution (pages 11001–11005)

      Dr. Manas K. Bhunia, Dr. Kazuo Yamauchi and Prof. Kazuhiro Takanabe

      Article first published online: 14 AUG 2014 | DOI: 10.1002/anie.201405161

      Thumbnail image of graphical abstract

      Trying out triazine: Crystalline carbon nitrides have been synthesized by employing supramolecular aggregation and ionic melt polycondensation. The triazine-based carbon nitride exhibits the excellent hydrogen evolution reaction rate at visible light and apparent quantum yield reaches about 7 % at 420 nm.

    26. Dinuclear Metal Complexes

      Facile C[BOND]H Bond Formation by Reductive Elimination at a Dinuclear Metal Site (pages 11006–11009)

      Dr. Richard D. Adams, Dr. Vitaly Rassolov and Yuen Onn Wong

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406219

      Thumbnail image of graphical abstract

      The electronically unsaturated dirhenium complex [Re2(CO)8(μ-AuPPh3)(μ-Ph)] was obtained from the reaction of [Re2(CO)8{μ-η2-C(H)[DOUBLE BOND]C(H)nBu}(μ-H)] with [Au(PPh3)Ph], and by reaction with HSnPh3 was converted into [Re2(CO)8(μ-H)(μ-Ph)] (see picture). This hydrido-bridged complex reductively eliminates benzene upon addition of NCMe.

    27. CO2 Utilization | Hot Paper

      Ruthenium-Catalyzed Reductive Methylation of Imines Using Carbon Dioxide and Molecular Hydrogen (pages 11010–11014)

      Dr. Kassem Beydoun, Ghazi Ghattas, Katharina Thenert, Prof. Dr. Jürgen Klankermayer and Prof. Dr. Walter Leitner

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201403711

      Thumbnail image of graphical abstract

      Tertiary N-methylamines were obtained in good to excellent yields through the reductive methylation of imines (used as such or formed in situ from amines and aldehydes, see scheme). Apart from the well-defined [Ru(triphos)(tmm)] catalyst, CO2 was used as the C1 source, and H2 as the reducing agent. This method enabled the preparation of the antifungal agent butenafine in one step with no apparent waste, thus increasing the atom efficiency of its synthesis.

    28. Microwave Spectroscopy

      Tautomerism in Neutral Histidine (pages 11015–11018)

      Celina Bermúdez, Santiago Mata, Dr. Carlos Cabezas and Prof. José L. Alonso

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201405347

      Thumbnail image of graphical abstract

      Conformational analysis: Neutral histidine has been generated in the gas phase by laser ablation of solid samples, and its NεH tautomeric form has been unraveled through its rotational spectrum (see picture). The quadrupole hyperfine structure, arising from the existing three 14N nuclei, constituted a site-specific probe for revealing the tautomeric form as well as the side-chain configuration of this proteogenic amino acid.

    29. Natural Products | Hot Paper

      One-Pot Enzymatic Synthesis of Merochlorin A and B (pages 11019–11022)

      Dr. Robin Teufel, Dr. Leonard Kaysser, Matthew T. Villaume, Dr. Stefan Diethelm, Mary K. Carbullido, Prof. Dr. Phil S. Baran and Prof. Dr. Bradley S. Moore

      Article first published online: 12 AUG 2014 | DOI: 10.1002/anie.201405694

      Thumbnail image of graphical abstract

      Assembly line: The biosynthetic pathway to merochlorins A and B was fully reconstituted in vitro and involves only four enzymes. The assembly route starts from the common metabolites dimethylallyl diphosphate, geranyl diphosphate, and malonyl CoA, which are transformed into an unusual polyketide-terpene hybrid intermediate. Oxidative chlorination and terpene cyclization complete the remarkably short pathway to the merochlorins.

    30. Natural Product Synthesis

      A Multitasking Vanadium-Dependent Chloroperoxidase as an Inspiration for the Chemical Synthesis of the Merochlorins (pages 11023–11026)

      Dr. Stefan Diethelm, Dr. Robin Teufel, Dr. Leonard Kaysser and Prof. Dr. Bradley S. Moore

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201405696

      Thumbnail image of graphical abstract

      Naturally inspiring: The vanadium- dependent chloroperoxidase Mcl24 was found to mediate a complex series of transformations in the biosynthesis of the merochlorins, in particular, a site-selective naphthol chlorination and an oxidative dearomatization/terpene cyclization sequence to build up the stereochemically complex carbon framework. Inspired by the enzyme reactivity, a chemical chlorination procedure paralleling the biocatalytic process was developed.

    31. Photoelectrodes

      Switchable Charge-Transfer in the Photoelectrochemical Energy-Conversion Process of Ferroelectric BiFeO3 Photoelectrodes (pages 11027–11031)

      Dr. Dawei Cao, Dr. Zhijie Wang, Nasori, Liaoyong Wen, Yan Mi and Prof. Yong Lei

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406044

      Thumbnail image of graphical abstract

      Poling station: The orientation of the BiFeO3 (BFO) band bending at the BFO/electrolyte in polycrystalline BFO photoelectrodes can be switched from upwards to downwards by poling pretreatments of +8 V or −8 V, respectively. It is thus possible to manipulate photoelectrochemical reactions on a single ferroelectric photoelectrode.

    32. Electrocatalysis | Hot Paper

      Controlling Selectivity in the Chlorine Evolution Reaction over RuO2-Based Catalysts (pages 11032–11035)

      Kai S. Exner, Josef Anton, Timo Jacob and Herbert Over

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406112

      Thumbnail image of graphical abstract

      Being selective: The selectivity in the industrially important Chlor-Alkali process has been elucidated on the microscopic level through a combination of DFT calculations and volcano plots. A single layer of TiO2(110) grown on RuO2(110) increases the selectivity between the chlorine and oxygen evolution reactions (CER and OER, respectively) by several orders of magnitude, while keeping the high activity for CER practically constant.

    33. Li-Ion Batteries | Very Important Paper

      Sustainable Electrical Energy Storage through the Ferrocene/Ferrocenium Redox Reaction in Aprotic Electrolyte (pages 11036–11040)

      Dr. Yu Zhao, Yu Ding, Dr. Jie Song, Dr. Gang Li, Prof. Guangbin Dong, Prof. John B. Goodenough and Prof. Guihua Yu

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406135

      Thumbnail image of graphical abstract

      The redox couple ferrocene/ferrocenium has been applied for the construction of a liquid cathode Li-ion redox battery for electrical energy storage. The redox reaction is highly reversible and efficient. Even after 250 full charge/discharge cycles the capacity maintains about 90 % of the initial value and the Coulombic efficiency reaches 98–100 %.

    34. Asymmetric Catalysis

      Kinetic Resolution of 1,1′-Biaryl-2,2′-Diols and Amino Alcohols through NHC-Catalyzed Atroposelective Acylation (pages 11041–11045)

      Dr. Shenci Lu, Si Bei Poh and Prof. Yu Zhao

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406192

      Thumbnail image of graphical abstract

      BINOL and NOBIN derivatives can be obtained in high enantioselectivities of ≥99 % ee through NHC-catalyzed kinetic resolution. This method presents the first highly enantioselective catalytic acylation of axially chiral alcohols.

    35. Isotopic Labeling

      A Universal Procedure for the [18F]Trifluoromethylation of Aryl Iodides and Aryl Boronic Acids with Highly Improved Specific Activity (pages 11046–11050)

      Dion van der Born, Claudia Sewing, Dr. J. (Koos) D. M. Herscheid, Prof. Dr. Albert D. Windhorst, Prof. Dr. Romano V. A. Orru and Dr. Danielle J. Vugts

      Article first published online: 26 AUG 2014 | DOI: 10.1002/anie.201406221

      Thumbnail image of graphical abstract

      A quality label: Tracers for positron emission tomography (PET) with a [18F]CF3 group directly attached to an arene were synthesized with improved specific activity by the trifluoromethylation of aryl iodides and aryl boronic acids with [18F]trifluoromethane (see scheme). In particular, the trifluoromethylation of aryl boronic acids proceeded rapidly under mild reaction conditions, thus making this method highly suitable for the production of PET tracers.

    36. Heterocycle Synthesis

      Dearomative Indole [5+2] Cycloaddition Reactions: Stereoselective Synthesis of Highly Functionalized Cyclohepta[b]indoles (pages 11051–11055)

      Guangjian Mei, Hao Yuan, Yueqing Gu, Wei Chen, Prof. Dr. Lung Wa Chung and Prof. Dr. Chuang-chuang Li

      Article first published online: 21 AUG 2014 | DOI: 10.1002/anie.201406278

      Thumbnail image of graphical abstract

      Bridge construction: The title reaction with an oxidopyrylium ylide resulted in efficient and diastereoselective construction of highly functionalized oxacyclohepta[b]indoles. The procedure proceeded under very mild reaction conditions, thus enabling high functional-group tolerance and endo selectivity. TBS=tert-butyldimethylsilyl, Tf=trifluoromethanesulfonyl.

    37. Photocatalysis

      Photocatalytic Synthesis of Dihydrobenzofurans by Oxidative [3+2] Cycloaddition of Phenols (pages 11056–11059)

      Travis R. Blum, Dr. Ye Zhu, Sarah A. Nordeen and Prof. Tehshik P. Yoon

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406393

      Thumbnail image of graphical abstract

      In a good light: The versatile photoredox properties of RuII chromophores offer a strategy to couple powerful oxidative transformations to benign inorganic peroxysulfate oxidants. In this example, the photocatalytic [3+2] cycloaddition of phenols and electron-rich styrenes for the synthesis of diverse dihydrobenzofurans is presented.

    38. Photochemistry

      Metal-Free C[BOND]H Bond Activation of Branched Aldehydes with a Hypervalent Iodine(III) Catalyst under Visible-Light Photolysis: Successful Trapping with Electron-Deficient Olefins (pages 11060–11064)

      Dr. Shin A. Moteki, Asuka Usui, Dr. Sermadurai Selvakumar, Dr. Tiexin Zhang and Prof. Dr. Keiji Maruoka

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406513

      Thumbnail image of graphical abstract

      A radical approach: The mild photocatalyzed activation of the C(O)[BOND]H bond in branched aldehydes offers easy access to acyl radicals and, without decarbonylation, allowed the efficient synthesis of unsymmetrical ketones by trapping with electrophilic olefins. A characteristic feature of this approach is the catalytic use of a hypervalent iodine(III) reagent to generate radicals.

    39. ortho Alkylation

      Iron-Catalyzed C(sp2)[BOND]H Alkylation of Carboxamides with Primary Electrophiles (pages 11065–11069)

      Brendan M. Monks, Erin R. Fruchey and Prof. Silas P. Cook

      Article first published online: 3 AUG 2014 | DOI: 10.1002/anie.201406594

      Thumbnail image of graphical abstract

      The direct­ ortho­ alkylation of 8-aminoquinoline-based aryl amides was achieved with primary alkyl bromides in high yields in the presence of an iron catalyst, 1,2-bis(diphenylphosphino)ethane (dppe), and PhMgBr in 2-MeTHF.

    40. Cross-Coupling

      Gold(I)-Catalyzed Diazo Coupling: Strategy towards Alkene Formation and Tandem Benzannulation (pages 11070–11074)

      Daming Zhang, Guangyang Xu, Dong Ding, Chenghao Zhu, Dr. Jian Li and Prof. Dr. Jiangtao Sun

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201406712

      Thumbnail image of graphical abstract

      Crossing paths: A gold(I)-catalyzed cross-coupling of diazo compounds to afford tetrasubstituted alkenes has been developed. In addition, a gold(I)-initiated benzannulation has been achieved in a tandem reaction involving cross-coupling of the vinyldiazoacetates, sequential 6π electrocyclization, and oxidative aromatization.

    41. Natural Product Synthesis

      Spiroacetal Formation through Telescoped Cycloaddition and Carbon–Hydrogen Bond Functionalization: Total Synthesis of Bistramide A (pages 11075–11078)

      Xun Han and Prof. Paul E. Floreancig

      Article first published online: 4 SEP 2014 | DOI: 10.1002/anie.201406819

      Thumbnail image of graphical abstract

      Actin' out: Spiroacetals can be prepared from aldehydes and functionalized dienes through a convergent, telescoped sequence of cycloaddition, oxidative C[BOND]H bond cleavage, and acid treatment. The functional-group tolerance and facile accessibility of the components render this procedure suitable for the synthesis of structurally complex natural products such as the actin-binding cytotoxin bistramide A.

    42. Sythetic Methods

      Regioselective Radical Aminofluorination of Styrenes (pages 11079–11083)

      Hongwei Zhang, Yongcheng Song, Dr. Jinbo Zhao, Prof. Jingping Zhang and Prof. Qian Zhang

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201406797

      Thumbnail image of graphical abstract

      Double agent: The copper-catalyzed radical aminofluorination of styrenes with N-fluorobenzenesulfonimide (NFSI) has been realized with high regioselectivity, thus affording aminofluorination products with regioselectivities opposite to those of the palladium-catalyzed and noncatalyzed processes. NFSI reacts under N[BOND]F bond homolysis and is utilized as both a radical nitrogen source and radical fluorine source.

    43. Cyclization

      Mild ArI-Catalyzed C(sp2)[BOND]H or C(sp3)[BOND]H Functionalization/C[BOND]O Formation: An Intriguing Catalyst-Controlled Selectivity Switch (pages 11084–11087)

      Xueqiang Wang, Joan Gallardo-Donaire and Prof. Ruben Martin

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201407011

      Thumbnail image of graphical abstract

      Who controls the switch? I! A tandem C(sp2)[BOND]H or C(sp3)[BOND]H functionalization/C[BOND]O bond-forming reaction catalyzed by IIII reagents generated in situ has been developed. The transformation shows broad scope under mild conditions and exhibits an unprecedented selectivity profile that can be switched depending on the nature of the iodine catalyst employed (see scheme; HFIP=1,1,1,3,3,3-hexafluoro-2-propanol).

    44. Cross-Coupling

      Synthesis of Direct β-to-β Linked Porphyrin Arrays with Large Electronic Interactions: Branched and Cyclic Oligomers (pages 11088–11091)

      Hao Cai, Keisuke Fujimoto, Dr. Jong Min Lim, Chaojie Wang, Weiming Huang, Yutao Rao, Senmiao Zhang, Hui Shi, Dr. Bangshao Yin, Prof. Dr. Bo Chen, Prof. Dr. Ming Ma, Prof. Dr. Jianxin Song, Prof. Dr. Dongho Kim and Prof. Dr. Atsuhiro Osuka

      Article first published online: 25 AUG 2014 | DOI: 10.1002/anie.201407032

      Thumbnail image of graphical abstract

      Molecular twine: The title porphyrin trimers and pentamers have been synthesized by Suzuki–Miyaura coupling of β-boryl-porphyrins and β-bromoporphyrins. The cyclic porphyrin trimer, the smallest directly linked cyclic porphyrin, and its twined pentamer exhibit small HOMO–LUMO gaps, broad nonsplit Soret bands, red-shifted Q-bands, and efficient excitation-energy hopping.

    45. Ruthenium Pincer Complexes | Hot Paper

      Direct Catalytic Olefination of Alcohols with Sulfones (pages 11092–11095)

      Dr. Dipankar Srimani, Dr. Gregory Leitus, Yehoshoa Ben-David and Prof. Dr. David Milstein

      Article first published online: 27 AUG 2014 | DOI: 10.1002/anie.201407281

      Thumbnail image of graphical abstract

      The one-step olefination of alcohols with sulfones for the direct synthesis of terminal and internal olefins can be catalyzed by ruthenium pincer complexes. Furthermore, performing the reaction with dimethyl sulfone under mild hydrogen pressure provides a one-step method for the replacement of alcohol hydroxy groups by methyl groups.

SEARCH

SEARCH BY CITATION