Angewandte Chemie International Edition

Cover image for Vol. 53 Issue 38

Early View (Online Version of Record published before inclusion in an issue)

Editor: Peter Gölitz, Deputy Editors: Neville Compton, Haymo Ross

Online ISSN: 1521-3773

Associated Title(s): Angewandte Chemie, Chemistry - A European Journal, Chemistry – An Asian Journal, ChemistryOpen, ChemPlusChem, Zeitschrift für Chemie

  1. Cover Pictures

    1. Bipolar Tribocharging Signal During Friction Force Fluctuations at Metal–Insulator Interfaces

      Dr. Thiago A. L. Burgo and Dr. Ali Erdemir

      Article first published online: 15 SEP 2014 | DOI: 10.1002/anie.201408559

      Thumbnail image of graphical abstract

      Friction force fluctuations are accompanied by two tribocharging events: the flow of charged species in one direction promptly followed by the flow of charges in the reverse direction. T. A. L. Burgo and A. Erdemir describe in their Communication (DOI: 10.1002/anie.201406541) that owing to mechanochemical reactions, a microscopically high-energy non-equilibrium steady state is formed at the interface triggering a triboplasma, with formation of electrostatic charges and emission of electromagnetic radiation.

  2. Communications

    1. Asymmetric Hydrogenation

      Nickel-Catalyzed Asymmetric Transfer Hydrogenation of Olefins for the Synthesis of α- and β-Amino Acids

      Dr. Peng Yang, Haiyan Xu and Prof. Dr. Jianrong (Steve) Zhou

      Article first published online: 15 SEP 2014 | DOI: 10.1002/anie.201407744

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      Nickel and dime for the asymmetric transfer hydrogenation of prochiral olefins to access α- and β-amino acids. Formic acid was used as the hydrogen source.

    2. Elusive Isomers

      Isomers of Disulfur Dinitride, S2N2

      Prof. Dr. Xiaoqing Zeng, Dr. Andrea Flores Antognini, Dr. Helmut Beckers and Prof. Dr. Helge Willner

      Article first published online: 15 SEP 2014 | DOI: 10.1002/anie.201407538

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      Two new open-shell S2N2 isomers, trans SNSN (3A′′) and cis SNSN (3A′′), as well as a closed-shell (SN)2 dimer (C2v, 1A1) are formed by UV photolysis (λ=248 or 255 nm) of cyclic S2N2 (1Ag) in solid Ar at 16 K. These isomers were characterized by their IR spectra and their mutual photo-interconversion reactions.

    3. Electron-Induced Decomposition

      Reactions in Nitroimidazole Triggered by Low-Energy (02 eV) Electrons: Methylation at N1-H Completely Blocks Reactivity

      Katrin Tanzer, Dr. Linda Feketeová, Benjamin Puschnigg, Prof. Dr. Paul Scheier, Prof. Dr. Eugen Illenberger and Prof. Dr. Stephan Denifl

      Article first published online: 15 SEP 2014 | DOI: 10.1002/anie.201407452

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      Low-energy electrons (LEEs) with energies of less than 2 eV effectively decompose the 4-nitroimidazole molecule by electron attachment. Thereby a variety of decomposition channels are observed involving simple bond cleavages but also complex reactions involving multiple bond cleavages and formation of new molecules. This rich chemistry induced by LEE is completely suppressed in the energy domain below 2 eV for the molecule in its methylated form.

    4. Nanocluster Self-Assembly

      Colloidal Self-Assembly of Catalytic Copper Nanoclusters into Ultrathin Ribbons

      Zhennan Wu, Dr. Yanchun Li, Jiale Liu, Prof. Zhongyuan Lu, Prof. Hao Zhang and Prof. Bai Yang

      Article first published online: 15 SEP 2014 | DOI: 10.1002/anie.201407390

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      Cooperative forces: Ligand-capped copper nanoclusters are self-assembled into ribbons with single-cluster thickness in colloidal solution, a process controlled by tuning the cooperation between the dipolar interaction between nanoclusters and the van der Waals attraction between ligands. The self-assembled structures exhibit excellent catalytic activity and durability in oxygen reduction reactions.

    5. Cluster Compounds

      π Aromaticity and Three-Dimensional Aromaticity: Two sides of the Same Coin?

      Dr. Jordi Poater, Prof. Dr. Miquel Solà, Prof. Dr. Clara Viñas and Prof. Dr. Francesc Teixidor

      Article first published online: 15 SEP 2014 | DOI: 10.1002/anie.201407359

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      Making the rules: The Wade–Mingos 4n+2 rule for three-dimensional closo boranes is equivalent to the Hückel (4n+2)π rule for two-dimensional polycyclic aromatic hydrocarbons.

    6. Target Identification

      Probing the Anticancer Mechanism of (−)-Ainsliatrimer A through Diverted Total Synthesis and Bioorthogonal Ligation

      Dr. Chao Li, Ting Dong, Qiang Li and Prof. Dr. Xiaoguang Lei

      Article first published online: 15 SEP 2014 | DOI: 10.1002/anie.201407225

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      The target of the structurally complex natural product (−)-ainsliatrimer A has been identified by a systematic and efficient approach enabled by diverted total synthesis and bioorthogonal ligation. This approach enabled visualization of the subcellular localization of the natural product in live cells and identified activation of PPARγ as leading to the anticancer activity of ainsliatrimer A.

    7. Reactive Intermediates

      Mechanistic Studies on the Rearrangement of 1-Alkenyl-2-alkynylcyclopropanes: From Allylic Gold(I) Cations to Stable Carbocations

      Dr. Eva Tudela, Jairo González, Dr. Rubén Vicente, Dr. Javier Santamaría, Prof. Dr. Miguel A. Rodríguez and Prof. Dr. Alfredo Ballesteros

      Article first published online: 15 SEP 2014 | DOI: 10.1002/anie.201407055

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      No longer elusive: The allylic gold(I) cation 2, which has been proposed as an intermediate in the rearrangement of alkynylcyclopropanes (1) into alkynylcyclohexadienes (3), has been detected and characterized by NMR spectroscopy. Participation of 2 was supported experimentally and theoretically, and through these studies, a stable homo-antiaromatic carbocation was isolated and characterized.

    8. Asymmetric Catalysis

      Iridium-Catalyzed Regio- and Enantioselective Allylic Substitution of Silyl Dienolates Derived from Dioxinones

      Ming Chen and Prof. John F. Hartwig

      Article first published online: 15 SEP 2014 | DOI: 10.1002/anie.201406778

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      Keep on ‘Troc'ing: The reported title reaction leads to the asymmetric allylation of a variety of allylic trichloroethyl carbonates with silyl dienolates. The γ-allylated products are produced selectively in 60–84 % yield and with 90–98 % ee. cod=1,5-cyclooctadiene, THF=tetrahydrofuran, TMS=trimethylsilyl.

    9. Remarkable Enhancement of Enantioselectivity in the Asymmetric Conjugate Addition of Dimethylzinc to (Z)-Nitroalkenes with a Catalytic [(MeCN)4Cu]PF6–Hoveyda Ligand Complex

      Dr. Xingzhong Zeng, Joe J. Gao, Dr. Jinhua J. Song, Dr. Shengli Ma, Dr. Jean-Nicolas Desrosiers, Dr. Jason A. Mulder, Dr. Sonia Rodriguez, Dr. Melissa A. Herbage, Dr. Nizar Haddad, Dr. Bo Qu, Dr. Keith R. Fandrick, Dr. Nelu Grinberg, Dr. Heewon Lee, Dr. Xudong Wei, Dr. Nathan K. Yee and Dr. Chris H. Senanayake

      Article first published online: 15 SEP 2014 | DOI: 10.1002/anie.201406247

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      Don’t forget Me! Challenging methyl-substituted all-carbon quaternary stereogenic centers were formed with high stereoselectivity by a copper-catalyzed asymmetric conjugate addition of Me2Zn to (Z)-nitroalkenes (see scheme; Bn=benzyl). The key feature is the unprecedented use of [(MeCN)4Cu]PF6 in conjunction with ligand L1 so that the undesired nitroalkene isomerization was minimized.

    10. Solid-State NMR Spectroscopy | Very Important Paper

      De Novo 3D Structure Determination from Sub-milligram Protein Samples by Solid-State 100 kHz MAS NMR Spectroscopy

      Dr. Vipin Agarwal, Susanne Penzel, Kathrin Szekely, Riccardo Cadalbert, Emilie Testori, Andres Oss, Jaan Past, Prof. Ago Samoson, Prof. Matthias Ernst, Dr. Anja Böckmann and Prof. Beat H. Meier

      Article first published online: 15 SEP 2014 | DOI: 10.1002/anie.201405730

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      Smaller and faster: The 3D structure of a model protein was determined with a protein sample one-fortieth of the usual amount thanks to 100 kHz magic-angle-spinning NMR spectroscopy.

    11. Oxidation Catalysis

      Catalytic Consequences of the Thermodynamic Activities at Metal Cluster Surfaces and Their Periodic Reactivity Trend for Methanol Oxidation

      Dr. Weifeng Tu and Prof. Ya-Huei (Cathy) Chin

      Article first published online: 15 SEP 2014 | DOI: 10.1002/anie.201405232

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      Oxidative dehydrogenation: The first-order rate coefficients for methanol oxidative dehydrogenation on metal clusters are a single-valued function of the O2/CH3OH ratio (see picture). The reactive collision frequency for CH3OH activation on O*-covered surfaces varies with the oxygen-binding strength in a classical volcano-type relation.

    12. Dissociation Dynamics

      State Selectivity and Dynamics in Dissociative Electron Attachment to CF3I Revealed through Velocity Slice Imaging

      Dr. Frímann H. Ómarsson, Prof. Dr. Nigel J. Mason, Prof. Dr. E. Krishnakumar and Prof. Dr. Oddur Ingólfsson

      Article first published online: 15 SEP 2014 | DOI: 10.1002/anie.201403859

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      The spin calls the shots: Velocity slice imaging was used to study the dynamics of electron-induced dissociation of the potential plasma gas CF3I (see picture). The changed spin state was found to switch the predominant diabatic path in the neutral CF3I molecule to an adiabatic path in the CF3 transient negative ion by opening a path through a conical intersection that is efficiently repressed by a required spin flip in the neutral molecule.

    13. Synthetic Methods

      Sustainable Three-Component Synthesis of Isothioureas from Isocyanides, Thiosulfonates, and Amines

      Pieter Mampuys, Dr. Yanping Zhu, Dr. Tjøstil Vlaar, Dr. Eelco Ruijter, Prof. Dr. Romano V. A. Orru and Prof. Dr. Bert U. W. Maes

      Article first published online: 15 SEP 2014 | DOI: 10.1002/anie.201406717

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      Safety first! A direct synthesis of isothioureas by a copper-catalyzed three-component reaction from readily available substrates (see scheme) avoids the toxic, flammable, and highly reactive reagents required in classical approaches. The reaction also enables the straightforward synthesis of S-aryl isothioureas, which are difficult to obtain by other methods.

    14. Self-Repairing Materials

      Self-Repairable Polyurethane Networks by Atmospheric Carbon Dioxide and Water

      Ying Yang and Prof. Marek W. Urban

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201407978

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      Self-repairing materials were obtained by reacting sugar moieties with hexamethylene diisocyanate trimer and polyethylene glycol to form cross-linked MGP-polyurethane networks. The repair process requires atmospheric amounts of CO2 and H2O, thus resembling plant behavior of carbon fixation during photosynthesis.

    15. Synthetic Methods

      Chiral Counteranion Strategy for Asymmetric Oxidative C(sp3)[BOND]H/C(sp3)[BOND]H Coupling: Enantioselective α-Allylation of Aldehydes with Terminal Alkenes

      Pu-Sheng Wang, Hua-Chen Lin, Yu-Jia Zhai, Zhi-Yong Han and Prof. Dr. Liu-Zhu Gong

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201408199

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      Go with the combo: The title reaction is realized by combining asymmetric counteranion catalysis and palladium-catalyzed allylic C[BOND]H activation. This method tolerates a wide scope of α-branched aromatic aldehydes and terminal alkenes, thus affording allylation products in high yields and with good to excellent levels of enantioselectivity.

    16. Cyclization

      Rhodium-Catalyzed Cyclization of Diynes with Nitrones: A Formal [2+2+5] Approach to Bridged Eight-Membered Heterocycles

      Dr. Chunxiang Wang, Dr. Dongping Wang, Hao Yan, Dr. Haolong Wang, Dr. Bin Pan, Dr. Xiaoyi Xin, Dr. Xincheng Li, Fan Wu and Prof. Dr. Boshun Wan

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201407394

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      Five-atom building unit: N-aryl-substituted nitrones were employed as five-atom coupling partners in the rhodium-catalyzed cyclization with diynes. In this reaction, the nitrone moiety served as a directing group for the catalytic C[BOND]H activation of the N-aryl ring. This formal [2+2+5] approach allows rapid access to bridged eight-membered heterocycles with broad substrate scope.

    17. Drug Delivery

      A Cancer-Targeted Nanosystem for Delivery of Gold(III) Complexes: Enhanced Selectivity and Apoptosis-Inducing Efficacy of a Gold(III) Porphyrin Complex

      Lizhen He, Prof. Dr. Tianfeng Chen, Yuanyuan You, Hao Hu, Dr. Wenjie Zheng, Dr. Wai-Lun Kwong, Taotao Zou and Prof. Dr. Chi-Ming Che

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201407143

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      Au gets carried away: Cancer-targeted mesoporous silica nanoparticles for delivery of cytotoxic gold(III) porphyrin complexes are prepared. Encapsulation of the metal complex minimizes its toxic side effects on normal human cells and enhances its anticancer efficacy through inhibition of thioredoxin reductase activity and activation of signaling pathways mediated by reactive oxygen species.

    18. Antimicrobial Peptides | Hot Paper

      Insect-Derived Proline-Rich Antimicrobial Peptides Kill Bacteria by Inhibiting Bacterial Protein Translation at the 70 S Ribosome

      Andor Krizsan, Dr. Daniela Volke, Stefanie Weinert, Prof.Dr. Norbert Sträter, Dr. Daniel Knappe and Prof.Dr. Ralf Hoffmann

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201407145

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      Lost in translation: Proline-rich antimicrobial peptides (PrAMPs) inhibit bacterial protein translation by binding to the 70S ribosome of Gram-negative bacteria. This represents a novel killing mechanism for gene-encoded antimicrobial peptides. Alanine substitutions in the peptides additionally identified specific basic and hydrophobic residues as major interaction sites, which will enable the design of optimized compounds.

    19. Photocatalysis

      Helical Graphitic Carbon Nitrides with Photocatalytic and Optical Activities

      Yun Zheng, Lihua Lin, Xiangju Ye, Fangsong Guo and Prof. Xinchen Wang

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201407319

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      Helical nanorods: Graphitic carbon nitride with helical nanorod-like morphology similar to spiral vines is constructed for artificial photosynthesis. This helically conjugated polymer can also be fabricated with opposite chirality and shows photocatalytic activity for water splitting and CO2 conversion.

    20. Synthetic Methods

      Visible-Light-Mediated 1,2-Acyl Migration: The Reaction of Secondary Enamino Ketones with Singlet Oxygen

      Weigang Fan and Dr. Pixu Li

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201407413

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      Singled out: Secondary enaminones were oxidized by photochemically generated singlet oxygen, and subsequent nucleophilic addition of an alcohol and with an 1,2-acyl migration afforded quaternary amino acid derivatives. An ene-type reaction pathway is proposed. It is distinctively different from the typical [2+2] addition of singlet oxygen to a C[DOUBLE BOND]C bonds.

    21. Natural Product Synthesis | Hot Paper

      Enantioselective Divergent Syntheses of Several Polyhalogenated Plocamium Monoterpenes and Evaluation of Their Selectivity for Solid Tumors

      Carl V. Vogel, Halina Pietraszkiewicz, Omar M. Sabry, Prof. William H. Gerwick, Dr. Frederick A. Valeriote and Prof. Christopher D. Vanderwal

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201407726

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      Glyceraldehyde acetonide serves as a chiral glyoxal equivalent and a linchpin for the enantioselective synthesis of several acyclic polyhalogenated monoterpenes from the red algae Plocamium. Several of these compounds demonstrate selective toxicity towards solid-tumor cell lines over leukemia cell lines, as well as low-micromolar cytotoxicity towards the HCT-116 human colon carcinoma cell line.

  3. Minireviews

    1. Asymmetric Synthesis

      The Asymmetric Hetero-Diels–Alder Reaction in the Syntheses of Biologically Relevant Compounds

      Vincent Eschenbrenner-Lux, Kamal Kumar and Prof. Dr. Herbert Waldmann

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201404094

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      The right tools: The hetero-Diels–Alder reaction is a powerful method for constructing six-membered aza- and oxa-ring systems. This Minireview provides an overview of the application of this reaction in the synthesis of natural products and other biologically relevant small molecules.

  4. Communications

    1. Orally Bioavailable Peptides

      Improving on Nature: Making a Cyclic Heptapeptide Orally Bioavailable

      Daniel S. Nielsen, Dr. Huy N. Hoang, Dr. Rink-Jan Lohman, Dr. Timothy A. Hill, Dr. Andrew J. Lucke, Prof. Dr. David J. Craik, Dr. David J. Edmonds, Dr. David A. Griffith, Charles J. Rotter, Dr. Roger B. Ruggeri, Dr. David A. Price, Dr. Spiros Liras and Prof. Dr. David P. Fairlie

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201405364

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      The oral absorption and bioavailability of a cyclic heptapeptide in rats was improved by combining heterocyclic constraints, intramolecular hydrogen bonds, and branched amino acid side chains to shield polar backbone atoms. These improvements were solely guided by amide H–D exchange rates, NMR-derived structures, and solvent-exposed polar surfaces.

    2. Homogeneous Catalysis

      Gold(I) Catalysis at Extreme Concentrations Inside Self-Assembled Nanospheres

      Dr. Rafael Gramage-Doria, Joeri Hessels, Stefan H. A. M. Leenders, Dr. Oliver Tröppner, Maximilian Dürr, Prof. Dr. Ivana Ivanović-Burmazović and Prof. Dr. Joost N. H. Reek

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201406415

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      A(u)ll in!! A self-assembly strategy which allows catalysis at extremely high local catalyst concentration inside a well-defined nanosphere is reported. The resulting intrinsically inactive gold(I) chloride complexes become catalytically active with high selectivities.

    3. C[BOND]H Activation

      Use of the Wilkinson Catalyst for the ortho-C[BOND]H Heteroarylation of Aromatic Amines: Facile Access to Highly Extended π-Conjugated Heteroacenes for Organic Semiconductors

      Yumin Huang, Prof. Dr. Di Wu, Jingsheng Huang, Qiang Guo, Juan Li and Prof. Dr. Jingsong You

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201406445

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      An old favorite that can’t be beat: An innovative system composed of the Wilkinson catalyst [Rh(PPh3)3Cl] and CF3COOH enabled the highly regioselective oxidative C[BOND]H/C[BOND]H cross-coupling of aromatic amines with heteroarenes (see scheme). The products could be conveniently transformed into highly extended π-conjugated heteroacenes with large HOMO–LUMO energy gaps and low-lying HOMO levels as promising organic semiconductors.

    4. Anthropogenic Contamination | Very Important Paper

      Tramadol—A True Natural Product?

      Dr. Souvik Kusari, Dr. Simplice Joel N. Tatsimo, Dr. Sebastian Zühlke, Dr. Ferdinand M. Talontsi, Prof. Dr. Simeon Fogue Kouam and Prof. Dr. Michael Spiteller

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201406639

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      The root of the problem: Tramadol, a synthetic analgesic, was recently detected in the roots of the Cameroonian medicinal plant Nauclea latifolia. However, tramadol is not a natural product. Along with its major mammalian metabolites, tramadol is present in the roots of N. latifolia and other plant species, as well as in soil and local water sources in the Far North region of Cameroon as a result of anthropogenic contamination.

    5. Adaptive Supramolecular Assemblies

      Adaptive Amphiphilic Dendrimer-Based Nanoassemblies as Robust and Versatile siRNA Delivery Systems

      Xiaoxuan Liu, Jiehua Zhou, Tianzhu Yu, Chao Chen, Qiang Cheng, Kheya Sengupta, Yuanyu Huang, Haitang Li, Cheng Liu, Yang Wang, Paola Posocco, Menghua Wang, Qi Cui, Suzanne Giorgio, Maurizio Fermeglia, Fanqi Qu, Sabrina Pricl, Yanhong Shi, Zicai Liang, Palma Rocchi, John J. Rossi and Ling Peng

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201406764

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      Vesicle-like dendrimersomes formed through the self-assembly of an amphiphilic dendrimer are able to undergo structural rearrangement into spherical micelles to entrap and condense siRNA into stable nanoparticles, which protect siRNA and promote siRNA delivery in various cells including human primary and stem cells as well as in vivo. This system combines the advantages of lipid and dendrimer vectors, hence constituting a novel and efficient siRNA delivery platform.

    6. Fluorescence Probes

      Protease Probes that Enable Excimer Signaling upon Scission

      Melanie Fischbach, Dr. Ute Resch-Genger and Prof. Dr. Oliver Seitz

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201406909

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      Let there be excimer light: Large Stokes shifts and the long lifetime of excimer emission facilitate measurements in optically dense, autofluorescent media such as blood serum. However, proteolytic cleavage abolishes rather than installs proximity relationships required for excimer signaling. Herein, we introduce a new approach which enables on-switching of pyrene excimer emission upon proteolytic scission of hairpin-shaped PNA-peptide probe.

    7. Zeolite Catalysis

      Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu-SSZ-13

      Christopher Paolucci, Anuj A. Verma, Dr. Shane A. Bates, Dr. Vincent F. Kispersky, Jeffrey T. Miller, Dr. Rajamani Gounder, Dr. W. Nicholas Delgass, Dr. Fabio H. Ribeiro and Dr. William F. Schneider

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201407030

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      Copper redox catalysis: Operando spectroscopy and density functional calculations isolate copper oxidation and reduction half-cycles during the selective reduction of NOx over a Cu-exchanged SSZ-13 zeolite catalyst containing only isolated CuII sites. NH3 and NO together reduce CuII to CuI ions, and each reduction event generates a CuI/H+ pair (see picture).

    8. Noble Metalates

      Alkaline Earth Guests in Polyoxopalladate Chemistry: From Nanocube to Nanostar via an Open-Shell Structure

      Peng Yang, Yixian Xiang, Zhengguo Lin, Bassem S. Bassil, Prof. Jie Cao, Linyuan Fan, Yanxuan Fan, Prof. Ming-Xing Li, Pablo Jiménez-Lozano, Dr. Jorge J. Carbó, Prof. Josep M. Poblet and Prof. Ulrich Kortz

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201407090

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      The noble template effect: The size of the alkaline earth metal ion guest (Ca2+, Sr2+, Ba2+) allows the shape and size of the resulting polyoxopalladate cluster to be tuned. The small Ca2+ ion leads to the 12-palladate nanocube, the large Ba2+ ion leads to the 15-palladate nanostar, and the intermediate-sized Sr2+ ion leads to an intermediary structure, an open-shell 12-palladate.

    9. Heterogeneous Catalysis

      Discovery of Highly Selective Alkyne Semihydrogenation Catalysts Based on First-Row Transition-Metallated Porous Organic Polymers

      Dr. Kristine K. Tanabe, Dr. Magali S. Ferrandon, Dr. Nathan A. Siladke, Dr. Steven J. Kraft, Guanghui Zhang, Dr. Jens Niklas, Dr. Oleg G. Poluektov, Dr. Susan J. Lopykinski, Dr. Emilio E. Bunel, Dr. Theodore R. Krause, Dr. Jeffrey T. Miller, Dr. Adam S. Hock and Dr. SonBinh T. Nguyen

      Article first published online: 12 SEP 2014 | DOI: 10.1002/anie.201405080

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      POP around: Six first-row transition metals can be engineered into active and selective catalysts for alkyne hydrogenation upon incorporation into catechol porous organic polymers (POPs). These results highlight the advantages of using a POP platform to develop new catalysts which are otherwise difficult to achieve through traditional heterogeneous and homogeneous routes.

    10. Carbon Nanofibers | Hot Paper

      Carbon Nanofibers Decorated with Molybdenum Disulfide Nanosheets: Synergistic Lithium Storage and Enhanced Electrochemical Performance

      Fei Zhou, Dr. Sen Xin, Dr. Hai-Wei Liang, Lu-Ting Song and Prof. Dr. Shu-Hong Yu

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407103

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      Carbon nanofibers (CNFs) decorated with molybdenum disulfide sheets are fabricated by a facile hydrothermal process with low-cost, biomass-derived carbonaceous nanofibers as the supports. On reacting with lithium, the nanofibers undergo novel electrochemical processes that are triggered by a synergistic lithium storage effect, leading to enhanced cycling and rate performance of the lithium-ion battery.

    11. Carbon Nanorings

      Intercrossed Carbon Nanorings with Pure Surface States as Low-Cost and Environment-Friendly Phosphors for White-Light-Emitting Diodes

      Xiaoming Li, Yanli Liu, Dr. Xiufeng Song, Dr. Hao Wang, Dr. Haoshuang Gu and Prof. Haibo Zeng

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201406836

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      Fluorescent nanomaterials: A one-step hydrothermal method to synthesize intercrossed carbon nanorings (see picture) with relatively pure hydroxy surface states is reported. The hydroxyl surface states make it possible to overcome aggregation-induced quenching effects and to emit scarce stable yellow-orange luminescence in both colloidal and solid states.

    12. Luminescent Organic Radicals

      Luminescence, Stability, and Proton Response of an Open-Shell (3,5-Dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl Radical

      Yohei Hattori, Dr. Tetsuro Kusamoto and Prof. Dr. Hiroshi Nishihara

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407362

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      Enhanced photostability: A luminescent open-shell organic radical with high chemical stability was synthesized. (3,5-Dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical (PyBTM) emits fluorescent light from the lowest doublet excited state and is up to 115 times more photostable than the previously reported luminescent radical tris(2,4,6-trichlorophenyl)methyl radical (TTM).

    13. Main-Group Chemistry

      Origin and Location of Electrons and Protons during the Formation of Intermetalloid Clusters [Sm@Ga3−xH3−2xBi10+x]3− (x=0, 1)

      Dipl.-Chem. Bastian Weinert, B.Sc. Fabian Müller, Dr. Klaus Harms, Dr. Rodolphe Clérac and Prof. Dr. Stefanie Dehnen

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407288

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      Desiring protons: The use of [GaBi3]2− in reactions with [Sm(C5Me4H)3] yielded the first protonated ternary intermetalloid clusters [Sm@Ga3−xH3−2xBi10+x]3− (x=0,1). By experimental and quantum chemical analyses, the presence of the Ga[BOND]H bonds was rationalized, and the transfer of electrons and protons during the formation process was elucidated.

    14. Sierpiński Triangles

      One-Step Multicomponent Self-Assembly of a First-Generation Sierpiński Triangle: From Fractal Design to Chemical Reality

      Rajarshi Sarkar, Kai Guo, Dr. Charles N. Moorefield, Prof. Mary Jane Saunders, Prof. Chrys Wesdemiotis and Prof. George R. Newkome

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407285

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      Mathematical mimicry leads to the synthesis of a Sierpiński triangle, which was obtained by multicomponent assembly and features terpyridine–CdII–terpyridine connectivity. Complementary ligand architecture and metal complex lability act in synergy to achieve the desired outcome.

    15. Heme Proteins

      Reverse Spin-Crossover and High-Pressure Kinetics of the Heme Iron Center Relevant for the Operation of Heme Proteins under Deep-Sea Conditions

      Dipl.-Chem. Oliver Troeppner, Dr. Rainer Lippert, Dr. Tatyana E. Shubina, Dr. Achim Zahl, Dr. Norbert Jux and Prof. Dr. Ivana Ivanović-Burmazović

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201406954

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      High-pressure chemistry: The effect of confined space was studied around a heme iron center (see picture). This effect is important for adaptation of microorganisms to extreme high-pressure conditions and for the design of spin switches that can operate in reverse mode.

    16. Polyketide Biosynthesis

      Enzymatic Polyketide Chain Branching to Give Substituted Lactone, Lactam, and Glutarimide Heterocycles

      Daniel Heine, Tom Bretschneider, Srividhya Sundaram and Prof. Dr. Christian Hertweck

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407282

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      Branching out: Applying the reconstituted β-branching module of the rhizoxin polyketide synthase to the in vitro biotransformation of synthetic polyketide mimics led to the stereoselective formation of substituted lactone, lactam, and glutarimide moieties. These findings not only illuminate the biosynthesis of glutarimide-bearing polyketides but also demonstrate the utility of this module for pathway engineering.

    17. Synthetic Methods

      Palladium(0)-Catalyzed Cross-Coupling of 1,1-Diboronates with Vinyl Bromides and 1,1-Dibromoalkenes

      Huan Li, Zhikun Zhang, Xianghang Shangguan, Shan Huang, Dr. Jun Chen, Dr. Yan Zhang and Prof. Dr. Jianbo Wang

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407000

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      It takes two B: The title reactions afford 1,4-dienes and allenes. These reactions utilize the high reactivities of both 1,1-diboronates and allylboron intermediates generated in the initial coupling reaction.

    18. Template Synthesis

      Supramolecular Transcription of Guanosine Monophosphate into Mesostructured Silica

      Dr. Carlos J. Bueno-Alejo, Dr. Luis A. Villaescusa and Dr. Alfonso E. Garcia-Bennett

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407005

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      Templates with a twist: Chiral guanosine monophosphate (GMP) has been used as a supramolecular template for the synthesis of highly ordered silica mesoporous materials with trigonal symmetry and anisotropic channels. Electron microscopy studies revealed diffuse scattering patterns (see picture) corresponding to silica modulations associated with the chiral twisting of the GMP tetramers.

    19. Biosensors | Very Important Paper

      Translating Bacterial Detection by DNAzymes into a Litmus Test

      Kha Tram, Pushpinder Kanda, Prof. Dr. Bruno J. Salena, Prof. Dr. Shuangyan Huan and Prof. Dr. Yingfu Li

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407021

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      A new way to use the litmus test: Cheap and widely available litmus dyes and pH papers have been used to achieve the detection of a bacterial pathogen (star) through the use of an RNA-cleaving DNAzyme (RCD), urease (Ur), and magnetic beads (MB). The method allowed the sensitive detection of E. coli in complex sample matrices such as apple juice, milk, and lake water.

    20. Supramolecular Gels

      Two-Component Supramolecular Gels Derived from Amphiphilic Shape-Persistent Cyclo[6]aramides for Specific Recognition of Native Arginine

      Youzhou He, Min Xu, Rongzhao Gao, Xiaowei Li, Fengxue Li, Xuedan Wu, Prof. Dingguo Xu, Dr. Huaqiang Zeng and Prof. Lihua Yuan

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407092

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      Picking and choosing: A supramolecular two-component gelation system based on the amphiphilic cyclo[6]aramide macrocycle and diethylammonium chloride is reported. This system provides a modularly tunable approach for creating functional two-component gel systems for highly specific recognition of L-arginine (L-Arg) from 19 other amino acids by competitive host–guest interactions.

    21. Reaction Mechanisms

      Kinetic, Spectroscopic, and Theoretical Assessment of Associative and Dissociative Methanol Dehydration Routes in Zeolites

      Andrew J. Jones and Prof. Enrique Iglesia

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201406823

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      Molecular crossroads: Associative routes prevail at low temperatures and high pressures for the reaction of methanol to dimethyl ether on zeolitic acids because they are mediated by larger transition states of lower enthalpy and entropy. A plausible sequence of elementary steps was established by rate and IR data during catalysis and confirmed by theoretical analysis using density functional theory with van der Waals interactions and transition-state theory formalisms.

    22. Carbohydrates

      From Chitin to Bioactive Chitooligosaccharides and Conjugates: Access to Lipochitooligosaccharides and the TMG-chitotriomycin

      Guillaume Despras, Aurélien Alix, Dominique Urban, Boris Vauzeilles and Jean-Marie Beau

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201406802

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      Short cuts from chitin: Deconstruction of chitin and selective reconstruction to give well-defined oligosaccharides provide an effective approach to bioactive glycoconjugates. This method was applied to the preparation of the important symbiotic glycolipids.

  5. Author Profiles

    1. Michael P. Doyle

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407119

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      I lose track of time when I’m solving a chemical problem. In retrospect I would never again take a job that removes me from research.

  6. Communications

    1. Structure Elucidation

      Switchable Amplification of Vibrational Circular Dichroism as a Probe of Local Chiral Structure

      Dr. Sérgio R. Domingos, M. Sc. Hans J. Sanders, Prof. Dr. František Hartl, Prof. Dr. Wybren J. Buma and Prof. Dr. Sander Woutersen

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407376

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      Turn ON the amp: Vibrational circular dichroism (VCD) signals of a spatially restricted part of a molecule can be detected by employing a local VCD amplifier that can be turned ON and OFF electrochemically. The amplification is localized in the neighborhood of the amplifier and can thus be used to locally probe chiral molecular structure.

    2. Electrochromic Supercapacitors | Hot Paper

      Large-Scale Fabrication of Pseudocapacitive Glass Windows that Combine Electrochromism and Energy Storage

      Peihua Yang, Peng Sun, Zhisheng Chai, Prof. Langhuan Huang, Dr. Xiang Cai, Prof. Shaozao Tan, Prof. Jinhui Song and Prof. Wenjie Mai

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407365

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      A pseudocapacitive glass window (15×15 cm2) is obtained by the deposition of WO3 on fluorine-doped tin oxide glass. Such smart pseudocapacitive glass windows show great potential in functioning as electrochromic windows and concurrently powering electronic devices, such as mobile phones or laptops.

  7. Obituaries

    1. Sheldon Shore (1930–2014)

      Prof. Dr. Malcolm H. Chisholm

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

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      Sheldon G. Shore, Distinguished Professor of Mathematical and Physical Sciences and Charles H. Kimberly Chair of Chemistry at The Ohio State University, died on April 4th, 2014. Shore’s research spanned vast areas of the periodic table but he is probably best known for his pioneering work on boron hydrides, metal carbonyl clusters, and lanthanide/transition-metal systems and their conversion to catalytically active nanoparticles.

    2. Helmut Knözinger (19352014)

      Prof. Michel Che and Prof. Gerhard Ertl

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407227

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      Professor Helmut Knözinger, an internationally leading scientist in catalysis and surface spectroscopy, died on Sunday January 14, 2014 in Munich. Knözinger developed the use of molecular probes to study catalytically active sites. He investigated a large number of catalytic reactions, with the goal of correlating the physicochemical characteristics of model catalysts with their catalytic properties in order to understand their function.

  8. Highlights

    1. Trifluoromethanide Anion

      The (Not So) Ephemeral Trifluoromethanide Anion

      Dr. Nico Santschi and Prof. Dr. Ryan Gilmour

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201408013

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      Conditions, conditions, conditions!” Prakash et al. recently described “the long-lived trifluoromethanide anion”, thus completing a story that began decades ago. The anion can be generated in relatively large quantities and can be fully characterized by variable-temperature NMR spectroscopy. This discovery is one in a long list of reactive intermediates isolated and characterized by the Prakash/Olah group.

  9. Editorials

    1. You have free access to this content
      C[BOND]H Functionalization: Collaborative Methods to Redefine Chemical Logic

      Prof. Huw M. L. Davies and Dr. Daniel Morton

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201406633

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      “… Ultimately through our scientific work and educational activities we aim to not only bring C[BOND]H functionalization to the mainstream attention of the chemical community, but also to train chemists who can take advantage of the benefits a collaborative network creates …” Read more in the Editorial by Huw M. L. Davies and Daniel Morton.

  10. Communications

    1. Biomass Conversion

      Solvent Effects in Acid-Catalyzed Biomass Conversion Reactions

      Max A. Mellmer, Dr. Canan Sener, Dr. Jean Marcel R. Gallo, Dr. Jeremy S. Luterbacher, Dr. David Martin Alonso and Prof. James A. Dumesic

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201408359

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      In acid-catalyzed biomass conversion (e.g., dehydration of xylose to furfural), the use of polar aprotic organic solvents, such as γ-valerolactone, affects the stabilization of the acidic proton relative to the protonated transition states. This leads to accelerated reaction rates and increased product selectivities compared to the transformations in aqueous media.

    2. Antitumor Agents | Hot Paper

      A CXCR4-Targeted Site-Specific Antibody–Drug Conjugate

      Dr. Sumith A. Kularatne, Dr. Vishal Deshmukh, Dr. Jennifer Ma, Dr. Virginie Tardif, Dr. Reyna K. V. Lim, Holly M. Pugh, Dr. Ying Sun, Anthony Manibusan, Aaron J. Sellers, Dr. Richard S. Barnett, Shailaja Srinagesh, Jane S. Forsyth, Dr. Wolf Hassenpflug, Dr. Feng Tian, Dr. Tsotne Javahishvili, Prof. Brunhilde Felding-Habermann, Prof. Brian R. Lawson, Dr. Stephanie A. Kazane and Prof. Peter G. Schultz

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201408103

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      Hitting the mark(er): A chemically defined anti-CXCR4–auristatin antibody–drug conjugate (ADC) was produced that selectively targets and eliminates CXCR4+ metastatic cancer cells in vitro and in vivo with no significant overt toxicity. Because the CXCR4 receptor is highly expressed in the majority of metastatic cancers, a CXCR4–auristatin ADC may be useful for the treatment of a variety of metastatic malignancies.

    3. Electrochemistry

      Simultaneous Detection of Single Attoliter Droplet Collisions by Electrochemical and Electrogenerated Chemiluminescent Responses

      Jeffrey E. Dick, Dr. Christophe Renault, Dr. Byung-Kwon Kim and Prof. Dr. Allen J. Bard

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407937

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      Shedding light on current events: A clear correlation between electrochemical and electrogenerated chemiluminescent (ECL) responses has been observed for collisions of nano- and micro-sized oil droplets on an ultra-microelectrode surface. The droplets serve as attoliter electrolysis reactors that, upon oxidation of the constituents within the droplet, display simultaneous current and ECL spikes. PMT=photomultiplier tube, TPrA=tri-n-propylamine.

    4. Amino Acids

      Sulfonamide-Promoted Palladium(II)-Catalyzed Alkylation of Unactivated Methylene C(sp3)[BOND]H Bonds with Alkyl Iodides

      Kai Chen and Prof. Dr. Bing-Feng Shi

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407848

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      Branching off: The title reaction of unactivated β-methylene C(sp3)[BOND]H bonds of α-amino acid substrates with alkyl iodides is described. The C(alkyl)– C(alkyl) bond-forming reaction proceeds in good yields, and by using sequential reactions β-branched amino acids can be obtained.

    5. Single-Chain Magnets

      Single-Chain Magnetic Behavior in a Hetero-Tri-Spin Complex Mediated by Supramolecular Interactions with TCNQF.− Radicals

      Dr. Zhao-Xi Wang, Xuan Zhang, Dr. Yuan-Zhu Zhang, Prof. Dr. Ming-Xing Li, Dr. Hanhua Zhao, Prof. Marius Andruh and Prof. Dr. Kim R. Dunbar

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407628

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      Stacking up single-chain magnets: A new route for the rational design of 1D magnetically bistable molecular materials has been exploited, in which the supramolecular π-stacking interactions between the 2p spins of TCNQF radicals (TCNQF=2-fluoro-7,7,8,8-tetracyano-p-quinodimethane) help to correlate the 3d–4f dinuclear anisotropic units and enhance the effective energy barrier for spin reversal.

    6. Cross-Coupling

      Copper-Catalyzed Coupling of Triaryl- and Trialkylindium Reagents with Aryl Iodides and Bromides through Consecutive Transmetalations

      Surendra Thapa, Dr. Santosh K. Gurung, Dr. Diane A. Dickie and Prof. Dr. Ramesh Giri

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407586

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      All-out cross-coupling: All three nucleophilic moieties of triorganoindium reagents can be transmetalated onto copper(I) catalysts in the presence of NaOMe, which enables the coupling with aryl iodides and bromides in a carbon–carbon bond-forming process. The transformation tolerates a wide range of functional groups and proceeds well with sterically hindered substrates and trialkylindium reagents.

    7. Halogen Bonding

      Iodide-Induced Shuttling of a Halogen- and Hydrogen-Bonding Two-Station Rotaxane

      Dr. Antonio Caballero, Laura Swan, Dr. Fabiola Zapata and Prof. Paul D. Beer

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407580

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      Set the wheel in motion: Halogen-bonding (XB) anion recognition is used to control the molecular motion of an interlocked structure. A novel XB–HB two-station rotaxane (HB=hydrogen bonding) is demonstrated to undergo shuttling of the macrocyclic wheel component from the HB to the XB station driven by iodide recognition whereas chloride binding results in the macrocycle residing at the HB station.

    8. Luminescence

      Bimetallic Cyclometalated Iridium(III) Diastereomers with Non-Innocent Bridging Ligands for High-Efficiency Phosphorescent OLEDs

      Dr. Yonghao Zheng, Dr. Andrei S. Batsanov, Dr. Mark A. Fox, Dr. Hameed A. Al-Attar, Khalid Abdullah, Dr. Vygintas Jankus, Prof. Martin R. Bryce and Prof. Andrew P. Monkman

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407475

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      Two phosphorescent dinuclear iridium(III) diastereomers are readily separated. The bridging diarylhydrazide ligand plays an important role in the electrochemistry and photophysics of the complexes. OLEDs using these complexes as green-emissive dopants have electroluminescence efficiencies (37 cd A−1, 11 % EQE) that are remarkably high for dinuclear metal complexes in a simple device architecture.

    9. Biosynthesis | Very Important Paper

      Chemical Probes for the Functionalization of Polyketide Intermediates

      Dr. Elena Riva, Dr. Ina Wilkening, Silvia Gazzola, W. M. Ariel Li, Dr. Luke Smith, Prof. Peter F. Leadlay and Dr. Manuela Tosin

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201407448

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      Towards novel “unnatural” products: Fermentation of ACP mutants of S. lasaliensis in the presence of functionalized chemical probes with subsequent site-selective modifications generates a library of nonnatural lasalocid A precursors and derivatives.

  11. Author Profiles

    1. Norio Shibata

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201406198

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      If I had one year of paid leave I would work for a Buddhist temple on a mountain whilst studying to become a priest. In a spare hour, I listen to “new wave” music.

  12. Communications

    1. Asymmetric Catalysis

      Nickel(II)-Catalyzed Asymmetric Propargyl and Allyl Claisen Rearrangements to Allenyl- and Allyl-Substituted β-Ketoesters

      Yangbin Liu, Haipeng Hu, Haifeng Zheng, Yong Xia, Prof. Dr. Xiaohua Liu, Dr. Lili Lin and Prof. Dr. Xiaoming Feng

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201404643

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      Oh, the O! Highly efficient catalytic asymmetric Claisen rearrangements of O-propargyl β-ketoesters and O-allyl β-ketoesters have been accomplished under mild reaction conditions. In the presence of the chiral N,N′-dioxide/NiII complex, a wide range of allenyl/allyl-substituted all-carbon quaternary β-ketoesters was obtained in generally good yield and high diastereoselectivity with excellent enantioselectivity. Tf=trifluoromethanesulfonyl.

    2. Nanoflakes | Hot Paper

      Hexagonal Transition-Metal Chalcogenide Nanoflakes with Pronounced Lateral Quantum Confinement

      Dr. Pere Miró, Jae Hyo Han, Prof. Dr. Jinwoo Cheon and Prof. Dr. Thomas Heine

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201404704

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      Six-sided flakes: Transition-metal dichalcogenide nanoflakes of composition MX2 (where M=Ti, Zr and Hf; X=S and Se) grow preferentially in equilateral hexagons and exhibit a pronounced lateral quantum confinement. The hexagonal shape arises from the charge location at the edges and vertices and the resulting Coulombic repulsion.

    3. Heterogeneous Catalysis

      Cu–Al Spinel Oxide as an Efficient Catalyst for Methanol Steam Reforming

      Dr. Hongjuan Xi, Xiaoning Hou, Yajie Liu, Shaojun Qing and Prof. Dr. Zhixian Gao

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201405213

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      Reforming reforming: Methanol steam reforming (MSR) was catalyzed by Cu–Al spinel oxide without prereduction. The catalysis is effectively initiated by the CuO phase present in CuAl2O4, which gradually releases active copper. Even the regenerated catalyst (CA2.5-900-R) was more active than the commercial Cu–Zn–Al (CZA) catalyst (see graph).

    4. Molecular Recognition

      Amine-Responsive Adaptable Nanospaces: Fluorescent Porous Coordination Polymer for Molecular Recognition

      Ritesh Haldar, Prof. Ryotaro Matsuda, Prof. Susumu Kitagawa, Prof. Subi J. George and Prof. Tapas Kumar Maji

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201405619

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      It all stacks up: A supramolecular host with a nano-coordination space built up by the assembly of a 1D coordination polymer has been synthesized for encapsulation and recognition of various aromatic amine guest molecules through an emission-readout process. In some cases, the charge-transfer emission is enhanced by energy transfer from the chromophoric naphthalene linker unit.

    5. N2 Cleavage and Formation

      Cleavage and Formation of Molecular Dinitrogen in a Single System Assisted by Molybdenum Complexes Bearing Ferrocenyldiphosphine

      Dr. Takamasa Miyazaki, Dr. Hiromasa Tanaka, Dr. Yoshiaki Tanabe, Dr. Masahiro Yuki, Dr. Kazunari Nakajima, Prof. Dr. Kazunari Yoshizawa and Prof. Dr. Yoshiaki Nishibayashi

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201405673

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      The N[TRIPLE BOND]N bond bridging two molybdenum complexes (see scheme) is cleaved by visible light to afford two molybdenum nitride complexes. Conversely, the bridging N2 is reformed by oxidation. Thus cleavage and formation of N2 is induced by two different external stimuli using a single system under ambient conditions.

    6. Molecular Diversity

      Synthesis of a Natural Product-Like Compound Collection through Oxidative Cleavage and Cyclization of Linear Peptides

      Dr. Rico Petersen, Dr. Sebastian T. Le Quement and Prof. Dr. Thomas E. Nielsen

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201405747

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      Complexity made simple: By harnessing the power of solid-phase peptide synthesis, readily available amino acid building blocks (monomers) were assembled into peptide sequences (oligomers) designed to undergo cascade reactions. Using simple reagents and reaction conditions, a collection of natural product-like compounds was synthesized, with excellent control of embedded scaffold stereocenters.

    7. Host–Guest Systems

      Control of Silver(I)–Dialkyl Chalcogenide Coordination by a Synthetic Cavity

      Dr. Yuh Kohyama, Dr. Takashi Murase and Prof. Dr. Makoto Fujita

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201406224

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      Complexed in a complex: Complexation of a silver(I) ion with dialkyl chalcogenides is performed in the cavity of a self-assembled cage. This method modulates the number and geometry of the chalcogenides coordinated to silver(I) and generates a metal–organic proximal state.

    8. Membrane Nanodiscs

      You have full text access to this OnlineOpen article
      Bacterial Reaction Centers Purified with Styrene Maleic Acid Copolymer Retain Native Membrane Functional Properties and Display Enhanced Stability

      Dr. David J. K. Swainsbury, Stefan Scheidelaar, Prof. Rienk van Grondelle, Prof. J. Antoinette Killian and Dr. Michael R. Jones

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201406412

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      Best of both worlds: Reaction centers purified from bilayer membranes using an amphipathic copolymer offer the experimental advantages of a detergent-solubilized membrane protein, but retain functional properties of the protein in the native bilayer. Under stress, reaction centers in copolymer–lipid nanodiscs are more robust than when housed in a detergent micelle or even the native membrane.

    9. Molecular Recognition

      A Fluorescence Nanosensor for Glycoproteins with Activity Based on the Molecularly Imprinted Spatial Structure of the Target and Boronate Affinity

      Dr. Wei Zhang, Wei Liu, Prof. Ping Li, Haibin Xiao, Dr. Hui Wang and Prof. Bo Tang

      Article first published online: 11 SEP 2014 | DOI: 10.1002/anie.201405634

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      An excellent fit: A fluorescence nanosensor based on the boronate affinity of the target was developed for the quantitative detection of glycoproteins. The recognition performance of the nanosensor, which was successfully used for the detection of horseradish peroxidase in biological fluids, was regulated by controlling the pH value and the temperature (see scheme).

    10. Chiral Nanostructures

      Nanospheres, Nanotubes, Toroids, and Gels with Controlled Macroscopic Chirality

      Sandra Arias, Dr. Félix Freire, Prof. Dr. Emilio Quiñoá and Prof. Dr. Ricardo Riguera

      Article first published online: 10 SEP 2014 | DOI: 10.1002/anie.201406884

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      Everything under control: Nanospheres, nanotubes, toroids, and gels are generated by the controlled aggregation of poly(aryl acetylenes) with left- or right-handed helicity with monovalent metal cations (Ag+, Li+, and Na+). The size and helicity of the nanostructures can be tuned, and the nanostructures were used to encapsulate a range of organic and inorganic substances.

    11. Organocatalysis

      Catalytic Enantioselective Alkylation of Sulfenate Anions to Chiral Heterocyclic Sulfoxides Using Halogenated Pentanidium Salts

      Lili Zong, Xu Ban, Choon Wee Kee and Prof. Dr. Choon-Hong Tan

      Article first published online: 10 SEP 2014 | DOI: 10.1002/anie.201407512

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      Phase transfer catalysis: Halogenated pentanidium salts are efficient phase-transfer catalysts for the enantioselective alkylation of sulfenate anions to sulfoxides with high enantioselectivity and high yield. Mechanistic studies indicate the ability of the catalysts to simultaneously activate/stabilize both nucleophile and electrophile through multiple noncovalent interactions (ion-pairing interaction, nonclassical hydrogen bonds, and halogen bonds).

    12. C[BOND]H Activation | Hot Paper

      Radical C[BOND]H Functionalization of Heteroarenes under Electrochemical Control

      Dr. Alexander G. O'Brien, Dr. Akinobu Maruyama, Dr. Yasuhide Inokuma, Prof. Makoto Fujita, Prof. Phil S. Baran and Prof. Donna G. Blackmond

      Article first published online: 10 SEP 2014 | DOI: 10.1002/anie.201407948

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      Electrochemical reactions are shown to be effective for the C[BOND]H functionalization of a number of heterocyclic substrates that are recalcitrant to conventional peroxide radical initiation conditions and of interest in medicinal chemistry. Monitoring reaction progress under electrochemical conditions provides mechanistic insight into the C[BOND]H functionalization process.

    13. Photoelectrochemistry

      Enhancement of Solar Hydrogen Evolution from Water by Surface Modification with CdS and TiO2 on Porous CuInS2 Photocathodes Prepared by an Electrodeposition–Sulfurization Method

      Dr. Jiao Zhao, Dr. Tsutomu Minegishi, Li Zhang, Dr. Miao Zhong, Gunawan, Dr. Mamiko Nakabayashi, Dr. Guijun Ma, Dr. Takashi Hisatomi, Dr. Masao Katayama, Prof. Dr. Shigeru Ikeda, Prof. Dr. Naoya Shibata, Prof. Dr. Taro Yamada and Prof. Dr. Kazunari Domen

      Article first published online: 10 SEP 2014 | DOI: 10.1002/anie.201406483

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      Porous photocathodes: CuInS2 porous films, prepared by sulfurization of electrodeposited metals and modified with thin layers of CdS and TiO2, evolved H2 from photoelectrochemical water reduction under simulated sunlight (see picture). The modified photocathodes showed a relatively high efficiency and stable H2 production under the reaction conditions by surface modification.

    14. Indole Chemistry

      Direct Oxidative Coupling of N-Acetyl Indoles and Phenols for the Synthesis of Benzofuroindolines Related to Phalarine

      Terry Tomakinian, Dr. Régis Guillot, Prof. Dr. Cyrille Kouklovsky and Dr. Guillaume Vincent

      Article first published online: 10 SEP 2014 | DOI: 10.1002/anie.201404055

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      Ironized! The unprecedented direct oxidative coupling between phenols and indole nuclei leading to the regioselective formation of the phalarine benzofuroindoline core is reported through the addition of phenoxy radicals to N-acetyl indoles mediated by FeCl3. DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone.

    15. Organocatalysis

      Anion-Binding Catalysis by Electron-Deficient Pyridinium Cations

      Prof. Dr. Albrecht Berkessel, Somnath Das, Daniel Pekel and Dr. Jörg-M. Neudörfl

      Article first published online: 10 SEP 2014 | DOI: 10.1002/anie.201403778

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      A successful Trio: Pyridinium cations carrying three electron-withdrawing substituents catalyze the alkylation of α-halo ethers with silyl ketene acetals through Coulombic anion binding. This C[BOND]C bond formation proceeds efficiently at low temperatures and at low catalyst loading.

  13. News

  14. Communications

    1. Bioinorganic Chemistry

      X-ray Emission Spectroscopy: A Spectroscopic Measure for the Determination of NO Oxidation State in Fe-NO Complexes

      Prof. Tsai-Te Lu, Dr. Tsu-Chien Weng and Prof. Wen-Feng Liaw

      Article first published online: 9 SEP 2014 | DOI: 10.1002/anie.201407603

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      Valence-to-core X-ray emission spectroscopy (V2C XES) probes the ΔEσ2s*-σ2p of iron-bound NO. This method serves as a spectroscopic measure for the quantitative determination of the NO oxidation state in Fe[BOND]NO complexes.

  15. News

  16. Communications

    1. Organocatalysis

      N-Heterocyclic Carbene Catalyzed Cyclocondensation of α,β-Unsaturated Carboxylic Acids: Enantioselective Synthesis of Pyrrolidinone and Dihydropyridinone Derivatives

      Xiang-Yu Chen, Zhong-Hua Gao, Chun-Yu Song, Chun-Lin Zhang, Prof. Dr. Zhi-Xiang Wang and Prof. Dr. Song Ye

      Article first published online: 9 SEP 2014 | DOI: 10.1002/anie.201407469

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      Into the mix: N-Heterocyclic carbenes (NHCs) catalyze the generation of α,β-unsaturated acyl azoliums from α,β-unsaturated carboxylic acids via in situ generated mixed anhydrides for the enantioselective [3+2] and [3+3] cyclocondensation with sulfonylated α-amino ketones and alkyl(aryl)imines, respectively. The corresponding pyrrolidinones and dihydropyridinones were isolated in good yields with high to excellent enantioselectivities.

    2. Allylrhodium Isomerization

      The Isomerization of Allylrhodium Intermediates in the Rhodium-Catalyzed Nucleophilic Allylation of Cyclic Imines

      Hamish B. Hepburn and Prof. Hon Wai Lam

      Article first published online: 9 SEP 2014 | DOI: 10.1002/anie.201407233

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      Rhodium dance: Allylrhodium species generated from potassium allyltrifluoroborates can undergo isomerization by a 1,4-rhodium(I) migration to give more complex isomers, which then react with cyclic imines to provide products with up to three new stereochemical elements. High enantioselectivities are obtained with chiral diene–rhodium complexes.

    3. Isotopic Labeling

      Acidity and Hydrogen Exchange Dynamics of Iron(II)-Bound Nitroxyl in Aqueous Solution

      Dr. Yin Gao, Abouzar Toubaei, Dr. Xianqi Kong and Prof. Dr. Gang Wu

      Article first published online: 9 SEP 2014 | DOI: 10.1002/anie.201407018

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      An acid test: The FeII-bound HNO is a very weak acid in aqueous solution with a pKa value of greater than 11. However, HNO undergoes rapid hydrogen exchange with water and the process is catalyzed by both acid and base.

    4. Water Oxidation

      Homogeneous Electrocatalytic Water Oxidation at Neutral pH by a Robust Macrocyclic Nickel(II) Complex

      Mei Zhang, Dr. Ming-Tian Zhang, Cheng Hou, Prof. Zhuo-Feng Ke and Prof. Tong-Bu Lu

      Article first published online: 9 SEP 2014 | DOI: 10.1002/anie.201406983

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      The first nickel-based homogeneous water oxidation catalyst has been reported, which can efficiently electrocatalyze water oxidation at neutral pH in phosphate buffer. The cis-conformation of the catalyst is the key active intermediate (see scheme; PCET=proton-coupled electron transfer).

    5. Carbon Dioxide | Hot Paper

      Differential Reduction of CO2 by Molybdenum and Vanadium Nitrogenases

      Johannes G. Rebelein, Prof. Dr. Yilin Hu and Prof. Dr. Markus W. Ribbe

      Article first published online: 9 SEP 2014 | DOI: 10.1002/anie.201406863

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      Vanadium nitrogenase can reduce CO2 to CO, CD4, C2D4, and C2D6. Its ability to reduce CO2 to C2 hydrocarbons adds another important reaction to the catalytic spectrum of the vanadium nitrogenase, that is, a reaction that involves C[BOND]C coupling from CO2.

    6. Photocatalysis

      Photocatalytic Hydrogen Production using Polymeric Carbon Nitride with a Hydrogenase and a Bioinspired Synthetic Ni Catalyst

      Dr. Christine A. Caputo, Manuela A. Gross, Dr. Vincent W. Lau, Dr. Christine Cavazza, Prof. Bettina V. Lotsch and Dr. Erwin Reisner

      Article first published online: 9 SEP 2014 | DOI: 10.1002/anie.201406811

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      Light harvesting: The noble metal-free photocatalytic hydrogen production system utilizes carbon nitride as a light-absorbing material in combination with a hydrogenase or a water-soluble synthetic bioinspired Ni catalyst. The stability of the carbon nitride leads to highly productive photocatalytic systems capable of sustained hydrogen production for more than 48 h for the semibiological system.

    7. Lithium Carbenoids

      Solid-State Structure of a Li/F Carbenoid: Pentafluoroethyllithium

      M. Sc. Benedikt Waerder, Dipl.-Chem. Simon Steinhauer, Beate Neumann, Dr. Hans-Georg Stammler, Dr. Andreas Mix, Dr. Yury V. Vishnevskiy, Prof. Dr. Berthold Hoge and Prof. Dr. Norbert W. Mitzel

      Article first published online: 9 SEP 2014 | DOI: 10.1002/anie.201406564

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      Despite its explosive nature crystals of the Li/F alkyl carbenoid pentafluoroethyllithium, LiC2F5, could be isolated and the first experimental structure of its ether adduct determined; this structure clarifies earlier speculations on structure–reactivity relationships in carbenoid chemistry.

    8. Pyrrole Synthesis | Hot Paper

      Insertion of Nitriles into Zirconocene-1-aza-1,3-diene Complexes: Chemoselective Synthesis of N-H and N-Substituted Pyrroles

      Shasha Yu, Meijun Xiong, Xin Xie and Prof. Yuanhong Liu

      Article first published online: 9 SEP 2014 | DOI: 10.1002/anie.201407221

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      Exercise control: N-H and N-substituted pyrroles can be prepared through the direct insertion of nitriles into zirconocene-1-aza-1,3-diene complexes and their subsequent acidic aqueous work-up. The outcome of the reaction depends on the relative stability and reactivity of the corresponding enamine–imine tautomers formed through the hydrolysis of the diazazirconacycles.

  17. Reviews

    1. Supramolecular Chemistry of Anions

      Advances in Anion Supramolecular Chemistry: From Recognition to Chemical Applications

      Dr. Nicholas H. Evans and Prof. Paul D. Beer

      Article first published online: 9 SEP 2014 | DOI: 10.1002/anie.201309937

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      Since the start of this millennium, anion supramolecular chemistry has evolved substantially beyond the chemistry of anion receptors. Alongside the research that continues on the binding and sensing of anions, large strides have been made in areas which have previously been underdeveloped, such as the use of anions as templates and for membrane transportation, and importantly in chemical applications including catalysis, ion extraction, and responsive molecular systems.

  18. Communications

    1. 2D Nanomaterials | Very Important Paper

      Nanocrystalline-Graphene-Tailored Hexagonal Boron Nitride Thin Films

      Kang Hyuck Lee, Dr. Hyeon-Jin Shin, Dr. Brijesh Kumar, Han Sol Kim, Jinyeong Lee, Dr. Ravi Bhatia, Dr. Sang-Hyeob Kim, In-Yeal Lee, Dr. Hyo Sug Lee, Prof. Gil-Ho Kim, Prof. Ji-Beom Yoo, Dr. Jae-Young Choi and Prof. Sang-Woo Kim

      Article first published online: 9 SEP 2014 | DOI: 10.1002/anie.201405762

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      A hexagonal boron nitride (h-BN) thin film with an atomically flat surface was obtained using unintentionally formed nanocrystalline graphene (nc-G). A wafer-scale dielectric h-BN thin film was synthesized on a bare sapphire substrate by assistance of nc-G, which prevented structural deformations during chemical vapor deposition. The sp3-hybridized edges of nc-G play a key role during these processes.

    2. Heterocycle Synthesis

      Palladium-Catalyzed Annulation of Diarylamines with Olefins through C[BOND]H Activation: Direct Access to N-Arylindoles

      Dr. Upendra Sharma, Dr. Rajesh Kancherla, Togati Naveen, Soumitra Agasti and Prof. Debabrata Maiti

      Article first published online: 9 SEP 2014 | DOI: 10.1002/anie.201406284

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      No group help needed: A palladium-catalyzed dehydrogenative coupling between diarylamines and olefins has been discovered for the synthesis of substituted indoles. This intermolecular annulation approach incorporates readily available olefins and obviates the need of any additional directing group. An ortho palladation, olefin coordination, and β-migratory insertion sequence has been proposed for the generation of an olefinated intermediate.

  19. Minireviews

    1. Upconversion

      Enhancing Luminescence in Lanthanide-Doped Upconversion Nanoparticles

      Sanyang Han, Dr. Renren Deng, Dr. Xiaoji Xie and Prof. Xiaogang Liu

      Article first published online: 9 SEP 2014 | DOI: 10.1002/anie.201403408

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      Lighten up: Light trapping by upconversion nanoparticles often suffers from low conversion efficiency because of the small absorption cross section and surface quenching effects of the nanoparticles. To this end, effective strategies have been developed to enhance upconversion luminescence, paving the way for new biological approaches and inexpensive energy conversion methods.

  20. Communications

    1. Natural Product Synthesis

      Synthesis of Bis(indole) Alkaloids from Arundo donax: The Ynindole Diels–Alder Reaction, Conformational Chirality, and Absolute Stereochemistry

      Dr. Jingjin Chen, Andrew J. Ferreira and Prof. Dr. Christopher M. Beaudry

      Article first published online: 8 SEP 2014 | DOI: 10.1002/anie.201407336

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      Conformational chirality: Bis(indole) alkaloids from Arundo donax were synthesized using the first ynindole Diels–Alder reaction. The alkaloids are chiral, having stable enantiomeric conformations with half-lives of racemization of t1/2=4150–25100 seconds at room temperature. Their absolute stereochemistry was determined using the exciton chirality method.

    2. C[BOND]H Activation

      Enantioselective C[BOND]H Bond Functionalization Triggered by Radical Trifluoromethylation of Unactivated Alkene

      Peng Yu, Jin-Shun Lin, Lei Li, Sheng-Cai Zheng, Ya-Ping Xiong, Li-Jiao Zhao, Prof. Dr. Bin Tan and Prof. Dr. Xin-Yuan Liu

      Article first published online: 8 SEP 2014 | DOI: 10.1002/anie.201405401

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      En route: The title redox-neutral reaction provides a convenient route to valuable enantioenriched trifluoromethylated N,O-aminals in good to excellent yields and with excellent regio-, chemo-, and enantioselectivity. The reaction features a CuI/Brønsted acid system and broad substrate scope.

    3. Bioinspired Materials

      Mussel-Inspired Dendritic Polymers as Universal Multifunctional Coatings

      Qiang Wei, Dr. Katharina Achazi, Hendrik Liebe, Andrea Schulz, Dr. Paul-Ludwig Michael Noeske, Dr. Ingo Grunwald and Prof. Dr. Rainer Haag

      Article first published online: 8 SEP 2014 | DOI: 10.1002/anie.201407113

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      Rapid and universal coatings were developed by mussel-inspired dendritic polyglycerol that mimics mussel foot proteins with regard to functional groups, molecular weight, and molecular structure. Multiple further modifications can be achieved by either pre- or post-functionalization and control of surface roughness.

    4. Perovskites

      Development of Double-Perovskite Compounds as Cathode Materials for Low-Temperature Solid Oxide Fuel Cells

      Seonyoung Yoo, Areum Jun, Dr. Young-Wan Ju, Dr. Dorj Odkhuu, Dr. Junji Hyodo, Prof. Hu Young Jeong, Prof. Noejung Park, Prof. Jeeyoung Shin, Prof. Tatsumi Ishihara and Prof. Guntae Kim

      Article first published online: 8 SEP 2014 | DOI: 10.1002/anie.201407006

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      Ca doping into the A site of NdBaCo2O5+δ (NBCO) leads to NdBa1−xCaxCo2O5+δ (NBCaCO), a new class of double-perovskite compounds that are highly stable under both air and CO2-containing atmosphere. They display fast oxygen ion diffusion and high catalytic activity toward oxygen reduction while they maintain excellent compatibility with the electrolyte.

    5. Carbohydrates

      Protecting-Group-Free One-Pot Synthesis of Glycoconjugates Directly from Reducing Sugars

      David Lim, Prof. Margaret A. Brimble, Dr. Renata Kowalczyk, Dr. Andrew J. A. Watson and Prof. Antony John Fairbanks

      Article first published online: 8 SEP 2014 | DOI: 10.1002/anie.201406694

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      Sugars get sticky in water: The combined use of ADMP and the Cu-catalyzed Huisgen cycloaddition allows the synthesis of a range of glycoconjugates directly from the corresponding reducing sugar in one step under aqueous conditions. The reaction is stereoselective and may be applied to the convergent synthesis of triazole-linked glycosides, oligosaccharides, and glycopeptides.

    6. Photochemical CO2 Reduction

      Selective Generation of Formamides through Photocatalytic CO2 Reduction Catalyzed by Ruthenium Carbonyl Compounds

      Dr. Katsuaki Kobayashi, Dr. Takashi Kikuchi, Prof. Susumu Kitagawa and Prof. Koji Tanaka

      Article first published online: 8 SEP 2014 | DOI: 10.1002/anie.201406553

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      Formamide generation: Photochemical CO2 reduction in the presence of a dialkyl amine and its ammonium salt affords a dialkyl formamide when a ruthenium carbonyl compound, [Ru(bpy)2(CO)2]2+, is used as a catalyst. Fast nucleophilic attack of the dialkyl amine on the Ru[BOND]CO scaffold with resulting formamide generation takes priority over the competing formation of formic acid.

    7. Microfluidics

      Tailoring of High-Order Multiple Emulsions by the Liquid–Liquid Phase Separation of Ternary Mixtures

      Martin F. Haase and Jasna Brujic

      Article first published online: 8 SEP 2014 | DOI: 10.1002/anie.201406040

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      Multiple droplets within droplets: Mapping of the phase diagram revealed a linear relationship between the diameters of concentric layers of multiple emulsions with an “onion” topology. The slope of the line depended on the initial composition of the ternary mixture and the molecular weight of the surfactant. This general rule quantitatively predicted the number of droplet layers and enabled the self-assembly of polymer capsules and liposomes.

    8. Functional Nanoparticles

      Thermoresponsive and Photoluminescent Hybrid Silicon Nanoparticles by Surface-Initiated Group Transfer Polymerization of Diethyl Vinylphosphonate

      M. Sc. Julian Kehrle, M. Sc. Ignaz M. D. Höhlein, Dr. Zhenyu Yang, M. Sc. Aljosha-Rakim Jochem, M. Sc. Tobias Helbich, Dr. Tobias Kraus, Prof. Dr. Jonathan G. C. Veinot and Prof. Dr. Bernhard Rieger

      Article first published online: 8 SEP 2014 | DOI: 10.1002/anie.201405946

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      Polymer–nanoparticle hybrids are synthesized using a rare earth metal catalyst. Applying surface-initiated group transfer polymerization, poly(diethyl vinylphosphonate) (PDEVP) is grafted from the silicon nanoparticle surface. The obtained products exhibit the coexistence of the bright photoluminescence of the silicon nanocrystals under UV irradiation and the thermoresponsive behavior of the PDEVP in water.

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