Chemistry - A European Journal

Cover image for Vol. 22 Issue 8

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

Editor: Neville Compton, Deputy Editors: Anne Deveson, Elisabeth Roedern

Impact Factor: 5.731

ISI Journal Citation Reports © Ranking: 2014: 22/157 (Chemistry Multidisciplinary)

Online ISSN: 1521-3765

Associated Title(s): Angewandte Chemie International Edition, Chemistry – An Asian Journal, ChemistryOpen, ChemistrySelect, ChemBioChem, ChemCatChem, ChemElectroChem, ChemMedChem, ChemPhysChem, ChemPlusChem, ChemSusChem, European Journal of Inorganic Chemistry, European Journal of Organic Chemistry

  1. Full Papers

    1. Luminescence

      Synthetic Control of the Excited-State Dynamics and Circularly Polarized Luminescence of Fluorescent “Push–Pull” Tetrathia[9]helicenes

      Yuki Yamamoto, Dr. Hayato Sakai, Dr. Junpei Yuasa, Prof. Yasuyuki Araki, Prof. Takehiko Wada, Prof. Tomo Sakanoue, Prof. Taishi Takenobu, Prof. Tsuyoshi Kawai and Prof. Taku Hasobe

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201504048

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      Controlled push–pull: A series of fluorescent “push–pull” thiahelicenes based on quinoxaline-fused tetrathia[9]helicene derivatives was synthesized to control the excited state dynamics and circularly polarized luminescence properties. The maximum ΦFL values of 0.43 and 0.30 were obtained in benzene.

    2. Mercury–Silver Sulfur Complexes

      Stable -ESiMe3 Complexes of CuI and AgI (E=S, Se) with NHCs: Synthons in Ternary Nanocluster Assembly

      Mahmood Azizpoor Fard, Tetyana I. Levchenko, Carolyn Cadogan, William J. Humenny and Prof. Dr. John F. Corrigan

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201503320

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      Marvel the silver–sulfur: Two sets of thermally stable, N-heterocyclic carbene metal–chalcogenolate complexes of the general formula [(IPr)Ag−ESiMe3] (IPr=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene; E=S, Se) and [(iPr2-bimy)Cu−ESiMe3]2 (iPr2-bimy=1,3-diisopropylbenzimidazolin-2-ylidene) are reported. These reagents can be used for the formation of mixed metal–chalcogenide clusters, including [(iPr2-bimy)6Cu10S8Hg3] , illustrated.

    3. Composite Materials

      One-Pot Synthesis of CoSex–rGO Composite Powders by Spray Pyrolysis and Their Application as Anode Material for Sodium-Ion Batteries

      Gi Dae Park and Prof. Yun Chan Kang

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201504398

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      Spray composites: A simple one-pot synthesis of metal selenide/reduced graphene oxide (rGO) composite powders by a spray pyrolysis process was developed (see figure). This process could be applied in the preparation of crumple-structured cobalt selenide/rGO composite powders with various compositions for applications including anode materials for sodium-ion batteries.

    4. Synthetic Methods | Hot Paper

      Alkaline-Earth-Catalysed Cross-Dehydrocoupling of Amines and Hydrosilanes: Reactivity Trends, Scope and Mechanism

      Clément Bellini, Dr. Vincent Dorcet, Prof. Dr. Jean-François Carpentier, Dr. Sven Tobisch and Dr. Yann Sarazin

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201504316

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      Ca, Sr and Ba complexes catalyse the highly active and chemoselective cross-dehydrocoupling of amines and hydrosilanes. The substrate scope (>30 products) includes diamines and di(hydrosilane)s (see figure). Key trends and mechanistic pathways were established by combining experimental and computational data.

    5. Host–Guest Systems

      Supramolecular Organization of Dye Molecules in Zeolite L Channels: Synthesis, Properties, and Composite Materials

      Dr. Pengpeng Cao, Dr. Oleg Khorev, Dr. André Devaux, Lucie Sägesser, Dr. Andreas Kunzmann, Prof. Achim Ecker, Prof. Robert Häner, Dr. Dominik Brühwiler, Prof. Gion Calzaferri and Prof. Peter Belser

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201504404

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      Rylenes in nanochannels: The synthesis and properties of organic dyes incorporated into zeolite L (ZL) crystals are described. The intercalation/insertion of 17 perylene diimides, 2 terrylene diimides, and 1 quaterrylene diimide into ZL is compared and their interactions with the inner surface of the ZL nanochannels are discussed (see figure).

    6. Synthetic Methods

      Synthesis and Applications of Silyl 2-Methylprop-2-ene-1-sulfinates in Preparative Silylation and GC-Derivatization Reactions of Polyols and Carbohydrates

      Prof. Dr. Dean Marković, Wandji Augustin Tchawou, Dr. Irina Novosjolova, Dr. Sylvain Laclef, Dr. Dmitrijs Stepanovs, Prof. Dr. Māris Turks and Prof. Dr. Pierre Vogel

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201504380

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      Regio- and chemoselective silylation of polyols and carbohydrates has been achieved by employing silyl sulfinates (see the picture; TBS=tert-butyldimethylsilyl, TES=triethylsilyl, TIPS=triisopropylsilyl, TMS=trimethylsilyl). The silylation reactions proceed in high yield because the reactions are mild and fast and produce only volatile byproducts. Furthermore, the silyl sulfinates are used as new derivatization reagents for the GC analysis of nonvolatile polyhydroxy compounds.

  2. Communications

    1. Synthetic Methods

      A New Approach for the Synthesis of Highly Substituted Aromatic Rings: The Alkyne-Mediated Approach

      Prof. Philip J. Parsons, Daniel R. Jones, Alex C. Padgham, Lewis A. T. Allen, Dr. Clive S. Penkett, Robert A. Green and Dr. Andrew J. P. White

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201504421

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      Rings in the microwave! Pentasubstituted aromatic rings serve as templates for drug design and can be conveniently prepared by the thermolysis of suitably substituted alkynes under microwave conditions.

  3. Full Papers

    1. Protein Folding

      Stereopositional Outcome in the Packing of Dissimilar Aromatics in Designed β-Hairpins

      Kamlesh Madhusudan Makwana and Dr. Radhakrishnan Mahalakshmi

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201504428

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      Flipping hairpins: Using various positional permutations of Trp/Tyr aromatic pairs in designed peptide β-hairpins, the benefits and drawbacks of stereopositional aryl permutations are described. A classic Edge-to-Face and Face-to-Edge geometry at proximal and distal aromatic pairs, respectively, is most stabilizing, with a twisted scaffold (see scheme, left). Stereopositional flipping of the aromatic pair can result in alternate aryl packing geometry with less stable scaffolds.

    2. Metal–Organic Frameworks

      A Luminescent Metal–Organic Framework Thermometer with Intrinsic Dual Emission from Organic Lumophores

      Hao Zhang, Dr. Chensheng Lin, Prof. Tianlu Sheng, Dr. Shengmin Hu, Chao Zhuo, Dr. Ruibiao Fu, Dr. Yuehong Wen, Haoran Li, Shaodong Su and Prof. Xintao Wu

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201504432

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      Cryogenic detection: The intrinsic photophysical property of cryogenic temperature can be taken advantage of to fabricate a luminescent metal–organic framework ratiometric thermometer (see structure) with dual emission arising from the Dexter energy transfer process between mixed organic lumophores.

    3. Sensors

      Electrospun Nanofibers from a Tricyanofuran-Based Molecular Switch for Colorimetric Recognition of Ammonia Gas

      Dr. Tawfik A. Khattab, Dr. Sherif Abdelmoez and Prof. Dr. Thomas M. Klapötke

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201504448

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      Nanofibrous ammonia sensor: A poly- (acrylic acid)–tricyanofuran–hydrazone nanofiber sensor for ammonia was fabricated by electrospinning. The colorimetric sensor (see figure) can detect ammonia at the parts per billion level in the solution phase and shows very good sensitivity. Ammonia sensing is reversible and the nanofibrous sensor can be reused several times.

    4. Frustrated Lewis Pairs

      Insertion Reactions of Neutral Phosphidozirconocene Complexes as a Convenient Entry into Frustrated Lewis Pair Territory

      Dr. Adrien T. Normand, Dr. Constantin G. Daniliuc, Birgit Wibbeling, Dr. Gerald Kehr, Prof. Pierre Le Gendre and Prof. Gerhard Erker

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201504792

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      Insertion of carbonyl compounds (CO2, aldehydes, ketones) into the Zr−P bond of phosphidozirconocene complexes provides easy access to new frustrated Lewis pairs (FLPs). These FLPs are useful in the synthesis of elaborate molecules, such as the depicted Zr/Fe/Pd trimetallic complex.

  4. Communications

    1. Thermal Energy Storage

      Confined-Volume Effect on the Thermal Properties of Encapsulated Phase Change Materials for Thermal Energy Storage

      Dr. Paula F. De Castro, Dr. Adham Ahmed and Prof. Dmitry G. Shchukin

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201505035

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      Encapsulating! The synthesis is described of new microcapsules based on n-docosane as a core and PU shells of three different sizes. The effect of the confined volume on the morphology, crystallinity, heat transfer, and the thermal stability properties of encapsulated n-docosane was demonstrated.

  5. Full Papers

    1. C−C Activation

      Highly Efficient Catalysis of Retro-Claisen Reactions: From a Quinone Derivative to Functionalized Imidazolium Salts

      Dr. Renso Visbal, Prof. Dr. Antonio Laguna and Prof. Dr. M. Concepción Gimeno

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201505095

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      A new and efficient method for the preparation of several imidazolium salts containing an ester group in the C4 position of the aromatic ring through a retro-Claisen reaction pathway is described. This new organic transformation takes place by the nucleophilic attack of an alcohol functionality over the carbonyl groups, thus promoting a double C−C bond activation (see scheme; Mes=mesityl).

  6. Cover Pictures

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      Supramolecular Wiring of Benzo-1,3-chalcogenazoles through Programmed Chalcogen Bonding Interactions

      Dr. Adrian Kremer, Dr. Andrea Fermi, Nicolas Biot, Prof. Johan Wouters and Prof. Dr. Davide Bonifazi

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201600199

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      A rational and convenient synthetic route for the preparation of stable 2-substituted benzo-1,3-chalcogenazoles is presented. The electron-depleted σ-holes on the chalcogen atoms are exploited to trigger programmed two- (X⋅⋅⋅Y) or three-atoms (X⋅⋅⋅Y⋅⋅⋅X) supramolecular interactions in the solid state; this gives wirelike structures in the presence of suitable N-containing ligands. More information can be found in the Full Paper by D. Bonifazi, et al. (DOI: 10.1002/chem.201504328).

  7. Communications

    1. Synthetic Methods

      Generation of an N[RIGHTWARDS ARROW]B Ladder-type Structure by Regioselective Hydroboration of an Alkenyl-Functionalized Quaterpyridine

      Markus Grandl, Dr. Yu Sun and Dr. Frank Pammer

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201600228

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      Two rungs at time: Taking advantage of an unusual regioselectivity, two boron centers are introduced into an oligopyridine though hydroboration. The effect of the resulting intramolecular N[RIGHTWARDS ARROW]B coordination on the molecular structure and the electronic properties are discussed (see scheme).

    2. Supramolecular Chemistry

      A Thermo- and Mechanoresponsive Cyano-Substituted Oligo(p-phenylene vinylene) Derivative with Five Emissive States

      Dr. Yoshimitsu Sagara, Anna Lavrenova, Dr. Aurélien Crochet, Dr. Yoan C. Simon, Prof. Katharina M. Fromm and Prof. Christoph Weder

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201600272

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      Penta-colored! Introduction of competing intermolecular interaction is a promising and effective way to achieve molecular materials with multicolored, stimuli-responsive luminescence behavior. Herein, a cyano-substituted oligo(p-phenylene vinylene) derivative that forms five different solvent-free solid-state molecular assemblies is described. The luminescence properties change upon thermal and mechanical stimuli (see figure).

  8. Cover Pictures

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      Activity Enhancement of G-quadruplex/hemin DNAzyme by Flanking d(CCC)

      Dr. Tianjun Chang, Dr. Hongmei Gong, Pi Ding, Dr. Xiangjun Liu, Dr. Weiguo Li, Dr. Tao Bing, Dr. Zehui Cao and Prof. Dr. Dihua Shangguan

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201600251

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      The flanked sequences containing d(CCC) on the core sequence of parallel G-quadruplexes improve the binding affinity of hemin to G-quadruplexes, thereby remarkably enhancing the activity of G-quadruplex/hemin DNAzyme and the hemin degradation by H2O2, as well as increasing the tolerance of DNAzyme to pH change. More information can be found in the Full Paper by D. Shangguan et al. (DOI: 10.1002/chem.201504797).

  9. Communications

    1. Metal–Organic Frameworks

      A Breathing Zirconium Metal–Organic Framework with Reversible Loss of Crystallinity by Correlated Nanodomain Formation

      Bart Bueken, Dr. Frederik Vermoortele, Dr. Matthew J. Cliffe, Dr. Michael T. Wharmby, Damien Foucher, Jelle Wieme, Dr. Louis Vanduyfhuys, Dr. Charlotte Martineau, Prof. Dr. Norbert Stock, Prof. Dr. Francis Taulelle, Prof. Dr. Veronique Van Speybroeck, Prof. Dr. Andrew L. Goodwin and Prof. Dr. Dirk De Vos

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201600330

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      Camouflaged from diffraction: The aliphatic isoreticular analogue of the well-known MOF UiO-66(Zr) undergoes a unique and reversible phase change upon guest removal. This change involves a topology-dictated loss of long-range order through the correlated formation of short-range ordered nanodomains.

  10. Cover Profiles

    1. Pillar[5]arene-Based Glycoclusters: Synthesis and Multivalent Binding to Pathogenic Bacterial Lectins

      Dr. Kevin Buffet, Dr. Iwona Nierengarten, Nicolas Galanos, Emilie Gillon, Dr. Michel Holler, Dr. Anne Imberty, Dr. Susan E. Matthews, Dr. Sébastien Vidal, Prof. Stéphane P. Vincent and Dr. Jean-François Nierengarten

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201600363

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      The results described in this paper clearly show the potential of pillar[5]arene scaffolds for the design of bioactive glycoclusters.” Read more about the story behind the cover in the Cover Profile and about the research itself on page ▪▪ ff. (DOI: 10.1002/chem.201504921).

  11. Cover Pictures

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      Pillar[5]arene-Based Glycoclusters: Synthesis and Multivalent Binding to Pathogenic Bacterial Lectins

      Dr. Kevin Buffet, Dr. Iwona Nierengarten, Nicolas Galanos, Emilie Gillon, Dr. Michel Holler, Dr. Anne Imberty, Dr. Susan E. Matthews, Dr. Sébastien Vidal, Prof. Stéphane P. Vincent and Dr. Jean-François Nierengarten

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201600405

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      The potential therapeutic applications of multivalent glycoclusters targeting bacterial adhesion lectins call for the design of core scaffolds presenting various valencies and topologies to understand the specificities of binding. Pillar[5]arenes are ideal candidates in this endeavor. More information can be found in the Full Paper by A. Imberty, S. Vidal, S. P. Vincent, and J.-F. Nierengarten, et al. (DOI: 10.1002/chem.201504921).

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      Cerium Complex-Catalyzed Oxidation of Arylmethanols under Atmospheric Pressure of Dioxygen and Its Mechanism through a Side-On μ-Peroxo Dicerium(IV) Complex

      Mitali Paul, Satoru Shirase, Dr. Yuma Morimoto, Dr. Laurent Mathey, Dr. Murugesapandian Balasubramanian, Dr. Shinji Tanaka, Prof. Dr. Shinobu Itoh, Prof. Dr. Hayato Tsurugi and Prof. Dr. Kazushi Mashima

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201600408

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      A cerium complex with a dianionic pentadentate ligand acted as a catalyst for aerobic oxidation of arylmethanols, in which a dinuclear cerium(IV) side-on peroxo complex was the key intermediate. The corresponding trivalent complex was able to activate dioxygen, and the oxidation proceeded catalytically under atmospheric pressure with inexpensive and environmentally friendly dioxygen as the primary oxidant. More information can be found in the Full Paper by K. Mashima, H. Tsurugi et al. (DOI: 10.1002/chem.201503846).

  12. Editorial

    1. Editorial

      You have free access to this content
      Building an Inclusive Culture in the Chemistry Department at Imperial College

      Prof. Tom Welton

      Article first published online: 11 FEB 2016 | DOI: 10.1002/chem.201600475

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      One of the main aims of any department is to appoint the very best chemists and to support them to reach their full potential. Success in this aim cannot look like a male to female ratio of professors of 20:1. In this Guest Editorial, T. Welton, Dean of the Faculty of Natural Sciences at Imperial College London, describes the processes introduced that led to the Chemistry Department at Imperial achieving a gold Athena SWAN award.

  13. Full Papers

    1. Electrochemistry

      Facile Synthesis of Nitrogen-Containing Mesoporous Carbon for High-Performance Energy Storage Applications

      Yunling Xu, Jie Wang, Zhi Chang, Bing Ding, Ya Wang, Laifa Shen, Changhuan Mi, Hui Dou and Prof. Xiaogang Zhang

      Article first published online: 5 FEB 2016 | DOI: 10.1002/chem.201503917

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      Nitrogen-doped mesoporous carbon: Nitrogen-containing mesoporous carbon (NMC) with a highly developed mesopore structure has been prepared through a facile one-step self-assembly process. Electrochemical studies have demonstrated it to be a promising electrode material for high-performance electrochemical double-layer capacitors (EDLCs) and Li-S batteries.

  14. Communications

    1. Zeolites

      Location of Framework Al Atoms in the Channels of ZSM-5: Effect of the (Hydrothermal) Synthesis

      Dr. Veronika Pashkova, Dr. Stepan Sklenak, Petr Klein, Dr. Martina Urbanova and Dr. Jiří Dědeček

      Article first published online: 5 FEB 2016 | DOI: 10.1002/chem.201503758

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      Where's Al? The location of Al in the channel system of ZSM-5 zeolites prepared using tetrapropylammonium cation (TPA+) as a structure-directing agent was analyzed. A majority of Al atoms are located at the channel intersection, regardless of variations of the Al and Si sources or the presence/absence of Na+ ions in the synthesis mixture (see figure).

  15. Full Papers

    1. Porphyrin Aggregates

      Porphyrin/Platinum(II) C^N^N Acetylide Complexes: Synthesis, Photophysical Properties, and Singlet Oxygen Generation

      Dr. Atanu Jana, Luke McKenzie, Dr. Ashley B. Wragg, Dr. Masatoshi Ishida, Dr. Jonathan P. Hill, Prof. Julia A. Weinstein, Dr. Elizabeth Baggaley and Prof. Dr. Michael D. Ward

      Article first published online: 5 FEB 2016 | DOI: 10.1002/chem.201504509

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      The photophysical, electrochemical, and light-induced singlet oxygen (1O2) generation properties are reported for a series of ZnII porphyrin–PtII C^N^N acetylide compounds. One, two, or three cyclometallated PtII C^N^N luminophores are grafted onto a ZnII porphyrin core (see figure; R=PEG chain).

    2. Cyanidophosphates

      Lewis-Acid-Catalyzed Synthesis of Cyanidophosphates

      Kevin Bläsing, Dr. Stefan Ellinger, Dr. Jörg Harloff, Prof. Dr. Axel Schulz, Katharina Sievert, Dr. Christoph Täschler, Dr. Alexander Villinger and Dr. Cornelia Zur Täschler

      Article first published online: 5 FEB 2016 | DOI: 10.1002/chem.201504523

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      Cyanido(fluorido)phosphates: Salts containing [PF6−n(CN)n] (n=1–4) ions were isolated on a preparative scale by utilizing Lewis acids (LA) catalysts under mild conditions (see equation). The best results with respect to purity, yield, and low cost were obtained when the F/CN substitution reactions were carried out in ionic liquids.

  16. Communications

    1. Nanotubes | Hot Paper

      Lipid Nanotube Tailored Fabrication of Uniquely Shaped Polydopamine Nanofibers as Photothermal Converters

      Dr. Wuxiao Ding, Dr. Svetlana A. Chechetka, Dr. Mitsutoshi Masuda, Dr. Toshimi Shimizu, Dr. Masaru Aoyagi, Dr. Hiroyuki Minamikawa and Dr. Eijiro Miyako

      Article first published online: 5 FEB 2016 | DOI: 10.1002/chem.201504958

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      Polydopamine (PDA) nanofibers with unique shapes were fabricated by using lipid nanotubes (LNT) as templates. A PDA-LNT hybrid with helically coiled PDA nanofibers showed morphological advantages in high light absorbance and photothermal conversion effect compared to a linear counterpart. This new type of PDA-LNT nanofiber hybrid could be useful in the development of various applications, such as biomedical technologies and sustainable energy materials.

    2. Polyoxometalates

      Water- and Temperature-Triggered Reversible Structural Transformation of Tetranuclear Cobalt(II) Cores Sandwiched by Polyoxometalates

      Yosuke Kuriyama, Dr. Yuji Kikukawa, Dr. Kosuke Suzuki, Dr. Kazuya Yamaguchi and Prof. Dr. Noritaka Mizuno

      Article first published online: 5 FEB 2016 | DOI: 10.1002/chem.201600139

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      Ch-ch-ch-ch-changes: Water- and temperature-triggered reversible structural transformation between cubane- and planar-type tetranuclear CoII cores was successfully demonstrated (see figure) within polyoxometalates, allowing dynamic manipulation of the magnetic and optical properties.

  17. Corrigenda

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      Corrigendum: Transport, Electrochemical and Thermophysical Properties of Two N-Donor-Functionalised Ionic Liquids

      Dr. Thomas Rüther, Assoc. Prof. Kenneth R. Harris, Michael D. Horne, Dr. Mitsuhiro Kanakubo, Dr. Theo Rodopoulos, Dr. Jean-Pierre Veder and Dr. Lawrence A. Woolf

      Article first published online: 5 FEB 2016 | DOI: 10.1002/chem.201505029

      This article corrects:

      Transport, Electrochemical and Thermophysical Properties of Two N-Donor-Functionalised Ionic Liquids

      Vol. 19, Issue 52, 17733–17744, Article first published online: 29 NOV 2013

  18. Cover Pictures

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      Fe0 Nanomotors in Ton Quantities (1020 Units) for Environmental Remediation

      Wei Zhe Teo, Prof. Radek Zboril, Dr. Ivo Medrik and Prof. Martin Pumera

      Article first published online: 5 FEB 2016 | DOI: 10.1002/chem.201600401

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      Bubble-propelled Fe0 Janus nanomotors show their potential as decontamination agents of pollutants in Indonesian coral reefs. Enhanced pollutant decomposition triggered by biocompatible Fe0 motors, which can be handled in air and fabricated in ton quantities for a low cost, will revolutionize the way the environmental remediation is carried out. More information can be found in the Full Paper by M. Pumera et al. (DOI: 10.1002/chem.201504912).

  19. Full Papers

    1. Luminescent Carbon Dots

      Influence of Inert and Oxidizing Atmospheres on the Physical and Optical Properties of Luminescent Carbon Dots Prepared through Pyrolysis of a Model Molecule

      Cláudia Emanuele Machado, Letícia Gazola Tartuci, Prof. Dr. Honória de Fátima Gorgulho, Prof. Dr. Luiz Fernando Cappa de Oliveira, Jefferson Bettini, Prof. Dr. Daniela Pereira dos Santos, Prof. Dr. Jefferson Luis Ferrari and Prof. Dr. Marco Antônio Schiavon

      Article first published online: 4 FEB 2016 | DOI: 10.1002/chem.201504234

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      Properties of C-dots: The physical and optical properties of carbon dots are closely related to the synthesis conditions and the employed precursor. The choice of the pyrolysis atmosphere for the carbonization of l-tartaric acid influences the final properties. The adjustments of their properties provide new nanomaterials suitable for future applications (see figure).

  20. Communications

    1. Supramolecular Chirality

      Induced Circular Dichroism in Phosphine Gold(I) Aryl Acetylide Urea Complexes through Hydrogen-Bonded Chiral Co-Assemblies

      Dr. Julien Dubarle-Offner, Dr. Jamal Moussa, Dr. Hani Amouri, Dr. Benjamin Jouvelet, Dr. Laurent Bouteiller and Dr. Matthieu Raynal

      Article first published online: 4 FEB 2016 | DOI: 10.1002/chem.201504441

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      Phosphine gold(I) aryl acetylide complexes equipped with a central bis(urea) moiety form hydrogen-bonded supramolecular polymers in solution that do not display any optical activity. Co-assembly with a chiral (metal-free) co-monomer is used to place the intrinsically achiral gold(I) aryl acetylide fragment in a chiral environment, as demonstrated by induced circular dichroism (ICD).

  21. Full Papers

    1. Synthetic Methods

      Synthesis of Natural and Unnatural Cyclooligomeric Depsipeptides Enabled by Flow Chemistry

      Daniel Lücke, Toryn Dalton, Prof. Steven V. Ley and Dr. Zoe E. Wilson

      Article first published online: 4 FEB 2016 | DOI: 10.1002/chem.201504457

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      Harnessing technology: Flow chemistry has been successfully integrated into the synthesis of a series of cyclooligomeric depsipeptides of three different ring sizes including the natural products beauvericin (1 a), bassianolide (2 b) and enniatin C (1 b), resulting in increased overall yields while decreasing the effort required for the researcher.

  22. Communications

    1. Natural Products

      Total Synthesis of 7,10-Epimer of the Proposed Structure of Amphidinolide N, Part I: Synthesis of the C1–C13 Subunit

      Dr. Koji Ochiai, Dr. Sankar Kuppusamy, Yusuke Yasui, Tsubasa Okano, Yasunobu Matsumoto, Dr. Nishant R. Gupta, Dr. Yohei Takahashi, Prof. Dr. Takaaki Kubota, Prof. Dr. Jun'ichi Kobayashi and Prof. Dr. Yujiro Hayashi

      Article first published online: 4 FEB 2016 | DOI: 10.1002/chem.201504674

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      Recent revision: Amphidinolide N, the structure of which has been recently revised, is a 26-membered macrolide featuring allyl epoxide and tetrahydropyran moieties with 13 chiral centers. Due to its challenging structure and extraordinary potent cytotoxicity, amphidinolide N is a highly attractive target of total synthesis. During the total synthesis studies of 7,10-epi-amphidinolide N, the C1–C13 subunit was synthesized enantio- and diastereoselectively .

    2. Total Synthesis of 7,10-Epimer of the Proposed Structure of Amphidinolide N, Part II: Synthesis of C17–C29 Subunit and Completion of the Synthesis

      Dr. Koji Ochiai, Dr. Sankar Kuppusamy, Yusuke Yasui, Kenji Harada, Dr. Nishant R. Gupta, Dr. Yohei Takahashi, Prof. Dr. Takaaki Kubota, Prof. Dr. Jun'ichi Kobayashi and Prof. Dr. Yujiro Hayashi

      Article first published online: 4 FEB 2016 | DOI: 10.1002/chem.201504675

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      RAMP linchpin: The total synthesis of 7,10-epimer of the proposed structure of amphidinolide N is described (see scheme). The requisite chiral C17–C29 subunit was assembled stereoselectively via Keck allylation, Shi epoxidation, diastereoselective 1,3-reduction, and a later oxidative synthesis of the THF framework. The C1–C13 and C17–C29 subunits were successfully coupled using a Enders RAMP “linchpin” as the C14–C16 three carbon unit, thereby controlling the chirality at C14 and C16.

  23. Full Papers

    1. Porous Nanostructures | Hot Paper

      Facilely Tuning Porous NiCo2O4 Nanosheets with Metal Valence-State Alteration and Abundant Oxygen Vacancies as Robust Electrocatalysts Towards Water Splitting

      Dr. Chengzhou Zhu, Shaofang Fu, Prof. Dan Du and Prof. Yuehe Lin

      Article first published online: 4 FEB 2016 | DOI: 10.1002/chem.201504739

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      Freestanding porous NiCo2O4 nanosheets with metal valence-state alteration and abundant oxygen vacancies were easily synthesized by electrodeposition following reduction treatment. The material may serve as a robust electrocatalyst for water splitting.

    2. Asphaltenes

      Synthesis and Aggregation Behavior of Chiral Naphthoquinoline Petroporphyrin Asphaltene Model Compounds

      Matthias Schulze, Dr. Alexander Scherer, Dr. Frank Hampel, Prof. Jeffrey M. Stryker and Prof. Rik R. Tykwinski

      Article first published online: 4 FEB 2016 | DOI: 10.1002/chem.201504683

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      Combining petroleum biomarkers: A naphthoquinoline moiety (formally a tetrahydro[4]helicene) fused to a steroid is tethered to NiII-porphyrins to form asphaltene model compounds (see figure). CD spectroscopy documents chirality in the porphyrin chromophore induced by the steroid group. Studies of axial coordination with pyridine show that changes in peripheral substitution results in significant changes in axial coordination, which is suggested to occur in natural asphaltenes.

  24. Communications

    1. Organic Chemistry

      Copper Hydride Catalyzed Reductive Claisen Rearrangements

      Kong Ching Wong, Elvis Ng, Wing-Tak Wong and Prof. Pauline Chiu

      Article first published online: 4 FEB 2016 | DOI: 10.1002/chem.201504870

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      Ireland–Claisen rearrangement: A reductive Claisen rearrangement has been developed using a readily available copper catalyst, ligand, and silane. The reaction features mild conditions, excellent yields, and good to excellent diastereoselectivities (see scheme).

  25. Full Papers

    1. Nanotechnology | Hot Paper

      Fe0 Nanomotors in Ton Quantities (1020 Units) for Environmental Remediation

      Wei Zhe Teo, Prof. Radek Zboril, Dr. Ivo Medrik and Prof. Martin Pumera

      Article first published online: 4 FEB 2016 | DOI: 10.1002/chem.201504912

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      Decontamination agents: In view of the demand for large-scale environmental remediation by micro-/nanomotors, which are easily synthesized and powered by nontoxic fuel, bubble-propelled Fe0 Janus nanomotors have been developed by a facile thermally induced solid-state procedure and their potential as decontamination agents of pollutants investigated (see figure).

    2. Click Chemistry | Hot Paper

      Pillar[5]arene-Based Glycoclusters: Synthesis and Multivalent Binding to Pathogenic Bacterial Lectins

      Dr. Kevin Buffet, Dr. Iwona Nierengarten, Nicolas Galanos, Emilie Gillon, Dr. Michel Holler, Dr. Anne Imberty, Dr. Susan E. Matthews, Dr. Sébastien Vidal, Prof. Stéphane P. Vincent and Dr. Jean-François Nierengarten

      Article first published online: 4 FEB 2016 | DOI: 10.1002/chem.201504921

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      A sweet pill: Pillar[5]arene-based glycoclusters with up to 20 peripheral sugars have been prepared by azide–alkyne “click” conjugations. Their binding properties have been studied for three bacterial lectins, namely LecA and LecB from Pseudomonas aeruginosa and BambL from Burkholderia ambifaria (see figure).

    3. Chemical Biology

      A Nitroxide-Tagged Platinum(II) Complex Enables the Identification of DNA G-Quadruplex Binding Mode

      Dr. Cui-Xia Xu, Dr. Xiaojun Zhang, Yi-Wei Zhou, Hanqiang Wang, Dr. Qian Cao, Dr. Yong Shen, Prof. Dr. Liang-Nian Ji, Prof. Dr. Zong-Wan Mao and Prof. Dr. Peter Z. Qin

      Article first published online: 4 FEB 2016 | DOI: 10.1002/chem.201504960

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      The groove armada: A dinuclear platinum(II) complex containing a nitroxide moiety (see structure) was synthesized and shown to specifically bind G-quadruplex DNA and inhibit telomerase activity. EPR and molecular docking analyses revealed that the complex binds to neighboring grooves in an antiparallel G-quadruplex. The work demonstrated a new strategy for developing small molecules for manipulating G-quadruplexes involved in crucial biological processes.

  26. Communications

    1. Homogeneous Catalysis

      Nickel-Catalyzed Cross-Coupling of Organolithium Reagents with (Hetero)Aryl Electrophiles

      Dorus Heijnen, Dr. Jean-Baptiste Gualtierotti, Dr. Valentín Hornillos and Prof. Dr. Ben L. Feringa

      Article first published online: 4 FEB 2016 | DOI: 10.1002/chem.201505106

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      Nickel-catalyzed cross-coupling of aromatic electrophiles with organolithium reagents is presented. The use of a commercially available nickel N-heterocyclic carbene complex allows reaction with a variety of (hetero)aryllithium compounds, whereas a commercially available electron-rich nickel bisphosphine complex smoothly converts alkyllithium species into the corresponding coupled product.

    2. Aromaticity

      [32]π Fused Core-Modified Heptaphyrin with Möbius Aromaticity

      Arindam Ghosh, Dr. Arvind Chaudhary, Dr. A. Srinivasan, Dr. Cherumuttathu H. Suresh and Prof. Dr. Tavarekere K. Chandrashekar

      Article first published online: 4 FEB 2016 | DOI: 10.1002/chem.201505116

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      First example of a 32π fused core-modified heptaphyrin, which exhibits Möbius aromaticity in solid, solution, and protonated state, is described. The rigid dithienothiophene (DTT) unit, flexible tripyrrane moiety, right combination of meso-aryl units, and reduction in the number of heteroatoms play major role to achieve this conformation (see figure).

    3. Nanotechnology | Hot Paper

      Graphitic C3N4-Sensitized TiO2 Nanotube Layers: A Visible-Light Activated Efficient Metal-Free Antimicrobial Platform

      Jingwen Xu, Yan Li, Xuemei Zhou, Yuzhen Li, Zhi-Da Gao, Yan-Yan Song and Patrik Schmuki

      Article first published online: 4 FEB 2016 | DOI: 10.1002/chem.201505173

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      Go nano! A facile procedure has been introduced to graft a thin g-C3N4 layer on aligned TiO2 nanotube arrays by a one-step chemical vapor deposition (CVD) approach. The formed g-C3N4/TiNT binary nanocomposite exhibits excellent bactericidal efficiency against E. coli as a visible-light-activated antibacterial coating (see figure).

    4. Porphyrinoids

      Chemo- and Regioselective Reduction of 5,15-Diazaporphyrins Providing Antiaromatic Azaporphyrinoids

      Ayaka Yamaji, Prof. Dr. Hayato Tsurugi, Prof. Dr. Yoshihiro Miyake, Prof. Dr. Kazushi Mashima and Prof. Dr. Hiroshi Shinokubo

      Article first published online: 3 FEB 2016 | DOI: 10.1002/chem.201600066

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      Reagent-controlled chemo- and regioselective reduction of 5,15-diazaporphyrins has been developed. The selective reduction of carbon–carbon double bonds of diazaporphyrins provides aromatic isobacteriochlorin-type products, whereas the reduction of carbon–nitrogen double bonds leads to N,N′-dihydrodiazaporphyrins with distinct antiaromatic character.

  27. Full Papers

    1. Porous Materials | Very Important Paper

      Metal–Organic Framework-Templated Porous Carbon for Highly Efficient Catalysis: The Critical Role of Pyrrolic Nitrogen Species

      Gang Huang, Li Yang, Xiao Ma, Prof. Dr. Jun Jiang, Prof. Dr. Shu-Hong Yu and Prof. Dr. Hai-Long Jiang

      Article first published online: 3 FEB 2016 | DOI: 10.1002/chem.201504867

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      Metal-free catalysis: Metal–organic frameworks (MOFs) are exploited as templates to afford porous carbon materials. Amongst these materials, PCN-224-templated carbon material optimized by pyrolysis at 700 °C exhibits a low activation energy and superior activity to other MOF-derived carbon materials and most metallic catalysts in the catalytic reduction of 4-nitrophenol to 4-aminophenol. Theoretical investigations suggest that the pyrrolic nitrogen species makes the dominant contribution to this activity (see figure).

  28. Communications

    1. Spiro Compounds

      Beyond the Dimer and Trimer: Tetraspiro[2.1.25.1.29.1.213.13] hexadecane-1,3,5,7-tetraone—the Cyclic Tetramer of Carbonylcyclopropane

      Dr. Kseniya N. Sedenkova, Dr. Elena B. Averina, Dr. Yuri K. Grishin, Kristian S. Andriasov, Svetlana A. Stepanova, Dr. Vitaly A. Roznyatovsky, Prof. Andrei G. Kutateladze, Dr. Victor B. Rybakov, Dr. Dmitry V. Albov, Dr. Tamara S. Kuznetsova and Prof. Nikolay S. Zefirov

      Article first published online: 3 FEB 2016 | DOI: 10.1002/chem.201600140

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      A way to rotane! Unknown cyclotetramer of carbonylcyclopropane was accessed from the parent hydrocarbon by the unprecedented oxidation of all four cyclopropane-activated methylenes (see scheme).

  29. Full Papers

    1. Layered Compounds

      K2Mn4O8/Reduced Graphene Oxide Nanocomposites for Excellent Lithium Storage and Adsorption of Lead Ions

      Shu-Meng Hao, Prof. Jin Qu, Jing Yang, Chen-Xi Gui, Qian-Qian Wang, Qian-Jie Li, Prof. Xiaofeng Li and Prof. Zhong-Zhen Yu

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504785

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      Active stacks: Layered K2Mn4O8/reduced graphene oxide (KMO/RGO) nanocomposites are fabricated through the anchoring of KMO nanoplates on RGO sheets (see figure). The nanocomposite with an optimal RGO content exhibits a higher first charging cycle capacity than that of KMO for use in lithium-ion batteries. For the adsorption of lead ions from water, the KMO/RGO nanocomposite exhibits a higher capacity than those of KMO and RGO alone.

    2. Amination

      Highly Regio- and Stereoselective Intermolecular Seleno- and Thioamination of Alkynes

      Guangfan Zheng, Jinbo Zhao, Zhanyu Li, Qiao Zhang, Jiaqiong Sun, Haizhu Sun and Qian Zhang

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504534

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      The first intermolecular chalcogenative amination reaction of alkynes is realized with N-fluorobenzenesulfonimide, which is used as both the oxidant and the amination reagent. The reaction features mild conditions, broad substrate scope, high levels of regioselectivity, and exclusive stereoselectivity. The reactions grant access to chalcogenated enamides in a very straightforward and atom-economical manner, and represent significant additions to the intermolecular aminative bisfunctionalization of alkynes.

  30. Communications

    1. Mixed Linkers

      A Simple and Non-Destructive Method for Assessing the Incorporation of Bipyridine Dicarboxylates as Linkers within Metal–Organic Frameworks

      Dr. Christopher H. Hendon, Jonathan Bonnefoy, Dr. Elsje Alessandra Quadrelli, Dr. Jerome Canivet, Dr. Matthew B. Chambers, Dr. Gwenaelle Rousse, Prof. Aron Walsh, Prof. Marc Fontecave and Dr. Caroline Mellot-Draznieks

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201600143

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      A close combination of computational chemistry, spectroscopy and laboratory X-ray diffraction allows access to a high-precision and non-destructive analysis of the genuine linker's incorporation into mixed-linker metal–organic frameworks (see figure). Our UV/Vis-based methodology has been further applied to characterize post-synthetically functionalized catalysts.

  31. Cover Pictures

    1. A Fluorination/Aryl Migration/Cyclization Cascade for the Metal-Free Synthesis of Fluoro-Benzoxazepines

      Anna Ulmer, Christoph Brunner, Andreas M. Arnold, Dr. Alexander Pöthig and Dr. Tanja Gulder

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201600133

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      The search for efficient fluorination methods, which ideally help to unlock new reactivities, is fueled by the importance of fluorinated molecules. With the bench-stable F-benziodoxole a new reagent has been established that reveals unexpected fluorination chemistry. Exemplified by the treatment of o-amide styrenes with the iodane, a new class of F-benzoxazepines became available furnished by a fluorination/migration/cyclization cascade. The chemoselective generation of these F-heterocycles is in clear contrast to the products obtained with the common F-reagents. More information can be found in the Communication by T. Gulder, et al. (DOI: 10.1002/chem.201504749).

  32. Communications

    1. Synthetic Chemistry

      Direct Catalytic Asymmetric Mannich-type Reaction of α,β-Unsaturated γ-Butyrolactam with Ketimines

      Shaoquan Lin, Dr. Naoya Kumagai and Prof. Dr. Masakatsu Shibasaki

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201600034

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      Ambident nucleophile! A direct catalytic asymmetric Mannich-type addition of α,β-unsaturated γ-butyrolactam to α-ethoxycarbonyl ketimines promoted by a soft Lewis acid/Brønsted base cooperative catalyst has been developed (see scheme; Ph-BPE=1,2-bis(2,5-dimethylphospholano)ethane). The obtained aza-Morita–Baylis–Hillman-type products bear an α-amino acid architecture with a tetra-substituted stereogenic center.

  33. Full Papers

    1. Amination

      Regioselective Synthesis of Quinazolinone-/Phenanthridine-Fused Heteropolycycles by Pd-Catalyzed Direct Intramolecular Aerobic Oxidative C−H Amination from Aromatic Strained Amides

      Dr. Biswadip Banerji, Suvankar Bera, Satadru Chatterjee, Sunil Kumar Killi and Saswati Adhikary

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504186

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      Fused rings: A novel approach to construct quinazolinone- and phenanthridine-fused pentacyclic compounds has been developed efficiently by a regioselective palladium-catalyzed C−H bond activation followed by an intramolecular amination of 2-biphenyl-2-yl-3H-quinazolin-4-ones.

    2. Porphyrin Chemistry

      Nickel(II) meso-Hydroxyporphyrin Complexes Revisited: Palladium-Catalysed Synthesis, Electronic Structures of Derived Oxy Radicals, and Oxidative Coupling to a Dioxoporphodimethene Dyad

      Dr. Louisa J. Esdaile, Dr. Llew Rintoul, Mean See Goh, Khalissa Merahi, Dr. Nathalie Parizel, Dr. R. Mark Wellard, Dr. Sylvie Choua and Prof. Dennis P. Arnold

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504252

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      Radically different porphyrins: Nickel(II) complexes of meso-hydroxy-15-phenyl-10,20-diarylporphyrins exist in solution in equilibrium with the corresponding oxy radicals (see figure), as shown by EPR spectra and the effects of addition of hydrazine on the NMR spectra. The analogous radicals without the 15-phenyl substituent are much less stable. The spin distributions have been modelled by DFT calculations.

  34. Communications

    1. Organic Synthesis

      Planar Chiral Phosphoramidites with Paracyclophane Scaffold: Synthesis, Gold(I) Complexes, and Enantioselective Cycloisomerization of Dienynes

      Zhiyong Wu, Kévin Isaac, Dr. Pascal Retailleau, Dr. Jean-François Betzer, Dr. Arnaud Voituriez and Dr. Angela Marinetti

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504658

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      The key structural feature of the new phosphoramidites is a paracyclophane scaffold in which two aryl rings are tethered by both a 1,8-biphenylene unit and a O−P−O bridge. Suitable aryl substituents generate planar chirality. Their gold(I) complexes promote the cycloisomerization of prochiral nitrogen-tethered dienynes to afford bicyclic derivatives with very high diastereoselectivity and up to 95 % ee (see scheme).

  35. Full Papers

    1. Porphyrinoids | Hot Paper

      2H-Tetrakis(3,5-di-tert-butyl)phenylporphyrin on a Cu(110) Surface: Room-Temperature Self-Metalation and Surface-Reconstruction-Facilitated Self-Assembly

      Dr. Liang Zhang, Michael Lepper, Michael Stark, Ralf Schuster, Dominik Lungerich, Prof. Dr. Norbert Jux, Prof. Dr. Hans-Peter Steinrück and Dr. Hubertus Marbach

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504214

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      Role of the substrate: 2H-Tetrakis(3,5-di-tert-butyl)phenylporphyrin (2HTTBPP) molecules can self-metalate with copper atoms from the substrate on both Cu(110) and Cu(110)–(2×1)O surfaces at room temperature (RT; see figure). The (2×1) surface reconstruction of Cu(110) by oxygen atoms also significantly modifies the molecule–substrate interaction and facilitates the self-assembly of 2HTTBPP molecules at RT.

    2. Graphene-Like Composites | Very Important Paper

      Construction of a 2D Graphene-Like MoS2/C3N4 Heterojunction with Enhanced Visible-Light Photocatalytic Activity and Photoelectrochemical Activity

      Dr. Jia Yan, Prof. Zhigang Chen, Dr. Haiyan Ji, Dr. Zheng Liu, Xin Wang, Dr. Yuanguo Xu, Dr. Xiaojie She, Dr. Liying Huang, Dr. Li Xu, Dr. Hui Xu and Prof. Huaming Li

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201503660

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      MoS2/C3N4 heterojunction: A new type of graphene-like MoS2/C3N4 composite has been prepared by a facile ethylene glycol-assisted solvothermal treatment. The synergistic effect of face-to-face combination increases the contact area and makes charge transfer more efficient, thereby promoting the separation of electron–hole pairs and leading to an enhancement of the overall photoconversion efficiency (see picture).

    3. Molecular Recognition

      Synthesis and Photophysical Studies of Calixarene-Based Alkynylplatinum(II) Terpyridine Complexes with Various Receptor Sites for Colorimetric and Luminescence Sensing of Anions

      Dr. Franky Ka-Wah Hau, Dr. Hiu-Suet Lo and Prof. Dr. Vivian Wing-Wah Yam

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201503401

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      Sense and sensitivity: The anion-binding properties of a series of mono- and dinuclear platinum(II) terpyridine complexes with amide-, sulfonamide- and urea-containing ligands were studied by electronic absorption, emission, and 1H NMR spectroscopy. Upon binding with anions, the dinuclear platinum(II) complexes exhibit large electronic absorption and emission spectral changes, together with interesting colorimetric response towards different anions, while for the mononuclear analogues much smaller spectral changes were observed.

    4. Fluorenes

      Tuning the Electronic Properties of Acetylenic Fluorenes by Phosphaalkene Incorporation

      Dr. Yurii V. Svyaschenko, Dr. Andreas Orthaber and Prof. Dr. Sascha Ott

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201503430

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      Bringing together the goodies: Fluorenes, acetylenes, and phoshosphaalkenes were combined in a novel class of compounds: acetylenic fluorene-9-ylidene phosphanes (F9Ps). Experimental and computational studies show that the exocyclic P center stabilizes the LUMO of the F9Ps and leads to significantly reduced HOMO–LUMO splittings. Variation of the acetylene substitution pattern is an additional tool to alter the optical and electronic properties.

    5. Surfactants

      Interaction Study and Reactivity of ZrIV-Substituted Wells–Dawson Polyoxometalate towards Hydrolysis of Peptide Bonds in Surfactant Solutions

      Thomas Quanten, Prof. Dr. Pavletta Shestakova, Dries Van Den Bulck, Prof. Dr. Christine Kirschhock and Prof. Dr. Tatjana N. Parac-Vogt

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201503976

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      K15H[Zr(α2-P2W17O61)2] and a range of surfactants were found, by means of NOESY and 1H and 31P DOSY, to interact with each other in an electrostatic manner. In addition, in the presence of these surfactants K15H[Zr(α2-P2W17O61)2] retained its catalytic nature towards the hydrolysis of the peptide bond in the dipeptide glycyl-l-histidine (see figure).

    6. Plasma Chemistry

      You have full text access to this OnlineOpen article
      Non-Thermal Plasma in Contact with Water: The Origin of Species

      Dr. Yury Gorbanev, Dr. Deborah O'Connell and Dr. Victor Chechik

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201503771

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      Cool plasma! The source of reactive oxygen species induced by non-thermal plasma in water has been investigated by UV, EPR and 1H NMR spectroscopy and MS in conjunction with the use of isotopically labelled water. The main regions in which species are formed are identified (see picture). An understanding of the fundamental properties of plasma is of paramount importance in applied biomedical plasma research.

    7. Aromatic Systems | Hot Paper

      Fused π-Extended Truxenes via a Threefold Borylation as the Key Step

      Dr. Gang Zhang, Dr. Frank Rominger and Prof. Dr. Michael Mastalerz

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504621

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      All from one: A diverse range of π- extended aromatic compounds (see scheme) are accessible in high-yielding two-step syntheses. The common starting point is a triborylated truxene precursor.

    8. Na Polysulfides

      Stable Crystalline Forms of Na Polysulfides: Experiment versus Ab Initio Computational Prediction

      Prof. Gregor Mali, Dr. Manu U. M. Patel, Dr. Matjaž Mazaj and Dr. Robert Dominko

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504242

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      Solids in Na–S batteries? Two tools for studying Na–S batteries are explored: ab initio crystal structure prediction for finding the potentially stable crystalline forms of sodium polysulfides and 23Na NMR spectroscopy for inspecting the composition of the batteries.

    9. Iterative Chemistry | Hot Paper

      Optimal ATRP-Made Soluble Polymer Supports for Phosphoramidite Chemistry

      Laurence Oswald, Dr. Abdelaziz Al Ouahabi, Prof. Dr. Laurence Charles and Dr. Jean-François Lutz

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504619

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      Designer supports: Soluble polystyrene (PS) supports with molecular structures specifically designed for phosphoramidite chemistry were synthesized, characterized, and tested for the iterative synthesis of sequence-coded oligophosphates. The supports were prepared by an efficient combination of atom-transfer radical polymerization and post- polymerization chain-end modification (see figure; DMT=dimethoxytrityl).

    10. Peptides | Very Important Paper

      Dual Chemical Modification of a Polytheonamide Mimic: Rational Design and Synthesis of Ion-Channel-Forming 48-mer Peptides with Potent Cytotoxicity

      Atsushi Hayata, Dr. Hiroaki Itoh, Shoko Matsutaka and Prof.Dr. Masayuki Inoue

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504632

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      Simpler but potent: Total synthesis and multiple functional analyses of seven new structurally simplified analogues of polytheonamide B, an ion-channel-forming 48-mer peptide, are reported. Structure–activity studies clarified that the bioactivity of the analogues can be rationally controlled by changing their hydrophobicity at residues 1 and 44 (see figure). The most hydrophobic analogue exhibited the highest cytotoxicity, which is almost as potent as that of polytheonamide B.

    11. Cyclopropanation Catalyst

      Design and Synthesis of Novel Chiral Dirhodium(II) Carboxylate Complexes for Asymmetric Cyclopropanation Reactions

      Dr. Frady G. Adly, Dr. Michael G. Gardiner and Dr. Ashraf Ghanem

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504817

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      Cyclopropanation catalyst: A series of dirhodium(II) tetracarboxylates derived from N-protected l-tert-leucine ligands have been prepared by tailoring the steric influences of the overall catalyst structure by reducing the local symmetry of the ligand's N-heterocyclic tether. Of these new complexes, [Rh2(S-tertPTTL)4] shows extraordinary selectivity as a catalyst in cyclopropanation reactions (see scheme) and is easy to synthesise compared with previously prepared dirhodium(II) catalysts of this type.

  36. Communications

    1. Lithium–Sulfur Batteries

      Biomass-Derived Porous Carbon with Micropores and Small Mesopores for High-Performance Lithium–Sulfur Batteries

      Kai Yang, Prof. Qiuming Gao, Yanli Tan, Weiqian Tian, Weiwei Qian, Lihua Zhu and Chunxiao Yang

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504672

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      Peel or no deal: A porous carbon prepared through pyrolysis of banana peel followed by activation with KOH displays high specific BET surface area, large specific pore volume, and well-controlled pore size distribution. Up to 65 wt % sulfur content could be loaded into the pores and, when the resultant C/S composite in used as the cathode of a Li–S battery, a large initial discharge capacity is obtained, alongside outstanding cycling stability.

  37. Full Papers

    1. Metal–Organic Frameworks | Hot Paper

      A Versatile CuII Metal–Organic Framework Exhibiting High Gas Storage Capacity with Selectivity for CO2: Conversion of CO2 to Cyclic Carbonate and Other Catalytic Abilities

      Dinesh De, Tapan K. Pal, Dr. Subhadip Neogi, S. Senthilkumar, Debasree Das, Dr. Sayam Sen Gupta and Prof. Parimal K. Bharadwaj

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504747

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      Storage and conversion combined: A novel NbO-type metal–organic framework LCu with pores decorated with NH2 groups exhibits notably high and selective storage of CO2 and its conversion to cyclic carbonate (see figure). Additionally, it can catalyze 1,3-dipolar cycloadditions as well as A3-coupling reactions.

    2. Frustrated Lewis Pairs | Very Important Paper

      You have full text access to this OnlineOpen article
      A Highly Reactive Geminal P/B Frustrated Lewis Pair: Expanding the Scope to C−X (X=Cl, Br) Bond Activation

      Kamil Samigullin, Isabelle Georg, Dr. Michael Bolte, Dr. Hans-Wolfram Lerner and Prof. Dr. Matthias Wagner

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504791

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      Complementary twins: The geminal frustrated Lewis pair tBu2PCH2B[3,5-(CF3)2C6H3]2 (1) is accessible from tBu2PCH2Li and [3,5-(CF3)2C6H3]2BF. Compound 1 readily activates element–element single, double, and triple bonds. Remarkably, CX4 undergoes C−X bond heterolysis with formation of unprecedented XP/BCX3 adducts (X=Cl, Br; see scheme).

    3. Heterogeneous Catalysis | Hot Paper

      Facile Synthesis, Characterization, and Catalytic Behavior of a Large-Pore Zeolite with the IWV Framework

      Dr. Joel E. Schmidt, Dr. Cong-Yan Chen, Stephen K. Brand, Dr. Stacey I. Zones and Prof. Mark E. Davis

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504717

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      Microporous materials: Synthesis of aluminosilicate IWV under industrially relevant conditions has been demonstrated, and the material can be produced in both fluoride and hydroxide media across a wide composition range. The zeolite demonstrates catalytic activity in the hydroisomerization of n-hexane (see figure).

    4. Synthetic Methods

      Generation of Aryl Radicals through Reduction of Hypervalent Iodine(III) Compounds with TEMPONa: Radical Alkene Oxyarylation

      Marcel Hartmann, Dr. Yi Li, Dr. Christian Mück-Lichtenfeld and Prof. Dr. Armido Studer

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504852

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      Clean radicals: Reduction of diaryliodonium salts and iodanylidene malonates with sodium 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPONa) allows for clean generation of aryl radicals (see scheme). Alkene oxyarylation is achieved when reduction is performed in the presence of an alkene radical acceptor.

    5. Gas-Phase Reactions

      Unravelling Mechanistic Aspects of the Gas-Phase Ethanol Conversion: An Experimental and Computational Study on the Thermal Reactions of MO2+ (M=Mo, W) with Ethanol

      Dr. Patricio González-Navarrete, Dr. Maria Schlangen, Dr. Xiao-Nan Wu and Prof. Dr. Helmut Schwarz

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504929

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      Similar gas-phase reactivity: The reactions of Mo and W dioxide cations with ethanol give rise to the dehydration of ethanol as the main product. The selectivity observed in the bulk phase for molybdenum and tungsten oxides with respect to oxidative dehydrogenation and dehydration of alcohols, respectively, is not reflected in the gas-phase, therefore, the selectivity may only arise in higher oxidation states, such as, for example, in MVI species.

  38. Communications

    1. Continuous-Flow Synthesis

      Continuous-Flow Microwave Synthesis of Metal–Organic Frameworks: A Highly Efficient Method for Large-Scale Production

      Dr. Marco Taddei, Daniel Antti Steitz, Prof. Dr. Jeroen Anton van Bokhoven and Dr. Marco Ranocchiari

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201505139

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      Panta rhei: Multigram-scale synthesis of benchmark metal–organic frameworks UiO-66, MIL-53(Al), and HKUST-1 was performed, resulting in outstanding performance. A continuous-flow microwave reactor was employed for this purpose.

    2. Host–Guest Systems

      Frozen Dissymmetric Cavities in Resorcinarene-Based Coordination Capsules

      Taisuke Imamura, Takeshi Maehara, Prof. Dr. Ryo Sekiya and Prof. Dr. Takeharu Haino

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201505183

      Thumbnail image of graphical abstract

      Coordination-driven self-assembly of cavitands in the presence of a chiral guest gave rise to a guest encapsulated capsule, resulting in a diastereoselectivity of >99 % de. The encapsulated guest was successfully removed from the chiral cavity, resulting in the nearly enantiopure capsule, the induced chirality of which was maintained for long periods in THF and 1,4-dioxane (see figure).

    3. Photocatalysis | Hot Paper

      Visible-Light-Mediated Photocatalytic Difunctionalization of Olefins by Radical Acylarylation and Tandem Acylation/Semipinacol Rearrangement

      Dr. Giulia Bergonzini, Dr. Carlo Cassani, Haldor Lorimer-Olsson, Johanna Hörberg and Dr. Carl-Johan Wallentin

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201504985

      Thumbnail image of graphical abstract

      Novel photoredox-mediated tandem radical acylarylation and tandem acylation/semipinacol rearrangement have been developed for the synthesis of highly functionalized ketones bearing an all-carbon α-quaternary center (see scheme). The method allows for a straightforward introduction of the keto functionality and concomitant construction of molecular complexity in a single operation.

  39. Full Papers

    1. Biosynthesis

      Discovery, Characterization, and Analogue Synthesis of Bohemamine Dimers Generated by Non-enzymatic Biosynthesis

      Dr. Peng Fu, Aaron Legako, Scott La and Prof. Dr. John B. MacMillan

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201600024

      Thumbnail image of graphical abstract

      A fortuitous dimerization: Three new dimeric bohemamine analogues dimerized through a methylene group were isolated from a marine-derived Streptomyces spinoverrucosus. The dimers can be formed through the semi-synthetic derivatization of monomeric bohemamines and formaldehyde under mild conditions. Furthermore, the formaldehyde could be detected in the culture. These results revealed that this dimerization is a non-enzymatic process (see scheme).

  40. Communications

    1. Helical Structures

      Assembly of an Achiral Chromophore into Light-Responsive Helical Nanostructures in the Absence of Chiral Components

      Prof. Dr. Mina Han, Prof. Dr. Sung June Cho, Dr. Yasuo Norikane, Prof. Dr. Masaki Shimizu and Prof. Dr. Takahiro Seki

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201600227

      Thumbnail image of graphical abstract

      The uncommon helical assembly of an achiral chromophore into fluorescent helical nanostructures in the absence of chiral components and the tunability of the helical pitch and fluorescence intensity in response to light are reported. A marked transformation from an achiral to an asymmetric molecule can occur as a result of specific interactions with certain solvents, presumably leading to the unique helical assembly.

    2. Total Synthesis

      Enantioselective Total Synthesis of (+)-Neostenine

      Yasuaki Nakayama, Yuichiro Maeda, Masayuki Kotatsu, Ruriko Sekiya, Masato Ichiki, Dr. Takaaki Sato and Prof. Dr. Noritaka Chida

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201600058

      Thumbnail image of graphical abstract

      18 steps to alkaloid! The first enantioselective total synthesis of (+)-neostenine by a chirality transfer approach using three sigmatropic rearrangements of acyclic polyol intermediates has been reported (see scheme). The sequential Overman/Claisen rearrangement was especially useful to introduce two contiguous stereocenters, including a carbon–nitrogen bond. The reaction took place in completely stereoselective fashion in a one-pot sequence.

    3. C−H Activation | Hot Paper

      Mechanistic Aspects of the Holmium-Mediated, Reciprocal Hydrogen/Sulfur Exchange in the Gas Phase: C6H5CH3+CH2S[RIGHTWARDS ARROW]C6H5CHS+CH4

      Dr. Shaodong Zhou, Dr. Jilai Li, Dr. Maria Schlangen and Prof. Dr. Helmut Schwarz

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201600061

      Thumbnail image of graphical abstract

      Hey Ho, here it goes: Ho+-mediated reaction of toluene with methanethial in the gas phase is reported. The mechanism involves the conversion of CH2S by Ho to ([Ho(CH2S)]+) which possesses a carbon radical and is capable of hydrogen-atom transfer from toluene; a sequence of hydrogen-atom abstractions combined with the making and breaking of covalent bonds are thus permitted (signals marked × are due to reactions with background contaminations).

    4. Supramolecular Chemistry

      A Supramolecular Chiral Auxiliary Approach: “Remote Control” of Stereochemistry at a Hierarchically Assembled Dimeric Helicate

      David Van Craen, Prof. Dr. Markus Albrecht, Prof. Dr. Gerhard Raabe, Fangfang Pan and Prof. Dr. Kari Rissanen

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201600158

      Thumbnail image of graphical abstract

      Far but not too far: A chiral auxiliary as well as an achiral reacting unit are statistically introduced in a hierarchically formed helicate. The Diels–Alder reaction with maleimides proceeds with moderate enantioselectivity with the dimer, whereas it is nearly switched off with the monomer (see scheme).

    5. Sensors

      A Molecular Imaging Approach to Mercury Sensing Based on Hyperpolarized 129Xe Molecular Clamp Probe

      Prof. Dr. Qianni Guo, Qingbin Zeng, Weiping Jiang, Xiaoxiao Zhang, Prof. Dr. Qing Luo, Prof. Dr. Xu Zhang, Prof. Dr. Louis-S. Bouchard, Prof. Dr. Maili Liu and Prof. Dr. Xin Zhou

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201600193

      Thumbnail image of graphical abstract

      In a pinch: A novel sensor is reported that is capable of yielding spatial distributions of mercury ions by MRI, using hyperpolarized 129Xe. This clamp probe (see figure) consists of dipyrrolylquinoxaline (DPQ) derivatives and two cryptophane-A cages. The DPQ derivatives act as cation receptors, whereas cryptophane-A acts as a suitable host molecule for xenon. This sensor exhibits good selectivity and sensitivity toward the mercury ions.

    6. Organic Chemistry

      Asymmetric Brønsted Base-Catalyzed and -Directed [3+2] Cycloaddition of 2-Acyl Cycloheptatrienes with Azomethine Ylides

      Vibeke H. Lauridsen, Lise Ibsen, Jakob Blom and Prof. Dr. Karl Anker Jørgensen

      Article first published online: 2 FEB 2016 | DOI: 10.1002/chem.201600255

      Thumbnail image of graphical abstract

      The first organocatalytic [3+2] cycloaddition reaction using a chiral cyclopropenimine Brønsted base as the catalyst has been reported. The reaction has been demonstrated to take place between a series of azomethine ylides and 2-acyl cycloheptatrienes in up to 90 % yield and 99 % ee (see scheme; Ts=tosyl, Bn=benzyl, Cy=cyclohexyl).

  41. Full Papers

    1. Metal–Organic Frameworks

      Hollow Zn/Co Zeolitic Imidazolate Framework (ZIF) and Yolk–Shell Metal@Zn/Co ZIF Nanostructures

      Christoph Rösler, Dr. Arshad Aijaz, Dr. Stuart Turner, Maria Filippousi, Azar Shahabi, Dr. Wei Xia, Prof. Dr. Gustaaf Van Tendeloo, Prof. Dr. Martin Muhler and Prof. Dr. Roland A. Fischer

      Article first published online: 28 JAN 2016 | DOI: 10.1002/chem.201503619

      Thumbnail image of graphical abstract

      An easy and reproducible method to synthesize hollow Zn/Co ZIF nanostructures (see figure; NP = nanoparticle) in a two-step protocol was developed. The strategy involves the targeted growth of a second ZIF on pre-synthesized ZIF-67 crystals with subsequent self-sacrifice/excavation of ZIF-67 to give nanocage-like materials.

  42. Communications

    1. Reactive Extraction

      Reactive Extraction of Lactic Acid by Using Tri-n-octylamine: Structure of the Ionic Phase

      Dr. Matthias Aimer, Prof. Dr. Elias Klemm, Dr. Bernd Langanke, Dr. Helmut Gehrke and Prof. Dr. Cosima Stubenrauch

      Article first published online: 28 JAN 2016 | DOI: 10.1002/chem.201503799

      Thumbnail image of graphical abstract

      The main extraction: Lactic acid is a promising biogenic platform chemical that can be produced by fermentation of cellulose and hemicellulose. Liquid/liquid extraction of lactic acid with tri-n-octylamine is investigated as a cost-effective alternative to the existing downstream processing method. To find an answer to this question, the structure of the middle phase of the occurring three-phase region, which is enriched with up to 20 wt. % lactic acid, is explored.

    2. Electroformation | Very Important Paper

      Point-to-Plane Nonhomogeneous Electric-Field-Induced Simultaneous Formation of Giant Unilamellar Vesicles (GUVs) and Lipid Tubes

      Chuntao Zhu, Ying Zhang, Yinan Wang, Qingchuan Li, Dr. Wei Mu and Prof. Dr. Xiaojun Han

      Article first published online: 28 JAN 2016 | DOI: 10.1002/chem.201504389

      Thumbnail image of graphical abstract

      Simultaneous formation of giant unilamellar vesicles (GUVs) and lipid tubes using a nonhomogeneous electric field generated by point-to-plane electrodes is reported. The figure shows a fluorescence image of the products under an AC field of 2.5 V and 10 Hz with an electrode distance of 340 μm (top) and the side view of the GUV electroformation setup (bottom).

  43. Full Papers

    1. Hydrogen Bonds

      Structure of Amido Pyridinium Betaines: Persistent Intermolecular C−H⋅⋅⋅N Hydrogen Bonding in Solution

      Dr. Robert J. Thatcher, Dr. David G. Johnson, Dr. John M. Slattery and Dr. Richard E. Douthwaite

      Article first published online: 28 JAN 2016 | DOI: 10.1002/chem.201503884

      Thumbnail image of graphical abstract

      C−H⋅⋅⋅N bonding: Unsupported C−H⋅⋅⋅N hydrogen bonding is observed in solution for the first time for N-heterocycles that are derived from norharman and related betaines. Thermodynamic parameters have been determined experimentally and theoretically to give an estimated C−H⋅⋅⋅N bond enthalpy of 7 kJ mol−1 (see figure).

  44. Communications

    1. Proton Transfer | Hot Paper

      Alcohol Dimer is Requisite to Form an Alkyl Oxonium Ion in the Proton Transfer of a Strong (Photo)Acid to Alcohol

      Dr. Sun-Young Park, Young Min Lee, Dr. Kijeong Kwac, Prof. Dr. Yousung Jung and Prof. Dr. Oh-Hoon Kwon

      Article first published online: 28 JAN 2016 | DOI: 10.1002/chem.201503948

      Thumbnail image of graphical abstract

      Dimer delights: The formation of an alkyl oxonium ion, a long-proposed intermediate in alcohol dehydration, is studied by time-resolved fluorescence quenching of a strong Brønsted photoacid. The collaboration of two alcohol molecules is found critical to enhance the reactivity and extract the proton from the acid.

  45. Full Papers

    1. Inorganic Chemistry | Very Important Paper

      Design and Syntheses of Three Novel Carbonate Halides: Cs3Pb2(CO3)3I, KBa2(CO3)2F and RbBa2(CO3)2F

      Lili Liu, Dr. Yun Yang, Dr. Xiaoyu Dong, Bingbing Zhang, Dr. Ying Wang, Prof. Zhihua Yang and Prof. Shilie Pan

      Article first published online: 28 JAN 2016 | DOI: 10.1002/chem.201504552

      Thumbnail image of graphical abstract

      Hello halide! Three novel carbonate halides, Cs3Pb2(CO3)3I (CPCI), KBa2(CO3)2F (KBCF) and RbBa2(CO3)2F (RBCF), have been synthesized through hydrothermal and solid-state methods (see figure). Cs3Pb2(CO3)3I, the first product in the lead carbonate iodide family, displays a moderate birefringence; KBa2(CO3)2F and RbBa2(CO3)2F are the first two centrosymmetric compounds found in the alkaline–alkaline earth carbonate fluorides.

    2. Reaction Mechanisms

      A Palladium-Catalyzed Carbonylation Approach to Eight-Membered Lactam Derivatives with Antitumor Activity

      Dr. Raffaella Mancuso, Dr. Dnyaneshwar S. Raut, Dr. Nadia Marino, Dr. Giorgio De Luca, Dr. Cinzia Giordano, Prof. Dr. Stefania Catalano, Dr. Ines Barone, Prof. Dr. Sebastiano Andò and Prof. Dr. Bartolo Gabriele

      Article first published online: 28 JAN 2016 | DOI: 10.1002/chem.201504443

      Thumbnail image of graphical abstract

      Making rings: A carbonylative ζ-lactamization approach to eight-membered heterocycles with an antiproliferative effect on MCF-7 and MDA-MB-231 tumor cells is reported (see scheme). It is based on the multicomponent oxidative cyclocarbonylation–alkoxycarbonylation of readily available 2-(2-ethynylphenoxy)anilines, catalyzed by the PdI42− complex under relatively mild conditions.

  46. Communications

    1. Amination

      Carboxylate-assisted Iridium-Catalyzed C−H Amination of Arenes with Biologically Relevant Alkyl Azides

      Tao Zhang, Xuejiao Hu, Zhen Wang, Tiantian Yang, Hao Sun, Prof. Guigen Li and Prof. Hongjian Lu

      Article first published online: 28 JAN 2016 | DOI: 10.1002/chem.201504880

      Thumbnail image of graphical abstract

      Ir responsible! A direct C−H amination between benzamide derivatives and various alkyl azides was achieved using iridium catalysis (see scheme; NTf=trifluoromethanesulfonyl amide). Cesium carboxylate was found to be the promoter and regiocontroller of this reaction. By this method, many biological active molecules can be introduced to benzamide components with high yields and 100 % chiral retention.

  47. Full Papers

    1. Bonding Analysis

      The Bond Order of C2 from an Strictly N-Representable Natural Orbital Energy Functional Perspective

      Prof. Mario Piris, Prof. Xabier Lopez and Prof. Jesus M. Ugalde

      Article first published online: 28 JAN 2016 | DOI: 10.1002/chem.201504491

      Thumbnail image of graphical abstract

      Order in the C2 court please! Calculations with the N-representable natural orbital functional PNOF5, complemented with size-consistent multiconfigurational perturbation theory corrections, PNOF5-PT2, reveal the complexity of the electronic structure of the ground state of C2 as illustrated by the existence of at least three different solutions that expand upon increasing internuclear distances. The inclusion of interpair correlation effects, PNOF6, leads to a continuous dissociation curve and a bond order for C2 intermediate between acetylene and ethylene.

  48. Communications

    1. Gold Complexes

      Gold(I) Vinylidene Complexes as Reactive Intermediates and Their Tendency to π-Backbond

      Laura Nunes dos Santos Comprido, Dr. Johannes E. M. N. Klein, Prof. Dr. Gerald Knizia, Prof. Dr. Johannes Kästner and Prof. Dr. A. Stephen K. Hashmi

      Article first published online: 28 JAN 2016 | DOI: 10.1002/chem.201504511

      Thumbnail image of graphical abstract

      Tight ion pair gold vinylidene complexes are studied as intermediates in the formation of vinyl sulfonates using computational methods (see scheme). The role of π-backbonding in gold vinylidene complexes, such as the aforementioned tight ion pair, is analysed by using the intrinsic bond orbital method.

  49. Minireviews

    1. Organic Synthesis

      Strategies for the Total Synthesis of Clavicipitic Acid

      Mamoru Ito, Yu-ki Tahara and Prof. Dr. Takanori Shibata

      Article first published online: 28 JAN 2016 | DOI: 10.1002/chem.201505014

      Thumbnail image of graphical abstract

      Intermediate is key: Clavicipitic acid is an ergot alkaloid with a unique tricyclic azepinoindole skeleton that has attracted many synthetic chemists. This Minireview summarizes the strategies for the total synthesis from the point of two key intermediates: 4-substituted gramine derivatives and 4-substituted tryptophan derivatives.

  50. Communications

    1. Metal–Organic Frameworks

      Cytotoxicity of Postmodified Zeolitic Imidazolate Framework-90 (ZIF-90) Nanocrystals: Correlation between Functionality and Toxicity

      Chia-I Yen, Szu-Mam Liu, Wei-Shang Lo, Jhe-Wei Wu, Yi-Hsin Liu, Prof. Rong-Jie Chein, Prof. Renqiang Yang, Prof. Kevin C.-W. Wu, Prof. Jih Ru Hwu, Prof. Nianhan Ma and Prof. Fa-Kuen Shieh

      Article first published online: 28 JAN 2016 | DOI: 10.1002/chem.201505005

      Thumbnail image of graphical abstract

      Supermodification: ZIF-90 (zeolitic imidazolate framework-90) nanocrystals were converted into carboxyl, amino, and thiol groups without affecting framework integrity. In vitro cytotoxicity assays reveals that the positively charged aminated ZIF-90 presumably results in perturbation of cell membrane and/or more efficient cell uptake. The half-maximal effective (EC50) concentration of aminated-ZIF-90 has a higher cytotoxicity (ca. 30 μg mL−1).

    2. Allene Hydroboration

      Olefin-Directed Palladium-Catalyzed Regio- and Stereoselective Hydroboration of Allenes

      Dr. Can Zhu, Bin Yang, Dr. Youai Qiu and Prof.Dr. Jan-E. Bäckvall

      Article first published online: 28 JAN 2016 | DOI: 10.1002/chem.201505130

      Thumbnail image of graphical abstract

      Direct chemistry: An olefin-directed palladium-catalyzed regio- and stereoselective hydroboration of allenes affording fully substituted alkenylboron compounds has been developed. The allyl C=C bond is a crucial directing group, and is responsible for the exclusive stereoselectivity. A series of functionalized allenes and alkyl-substituted allenes underwent this transformation (see scheme).

    3. Substituent Effects | Hot Paper

      Fine Substituent Effects in Sandwich Complexes: A Threshold Ionization Study of Monosubstituted Chromium Bisarene Compounds

      Prof. Dr. Sergey Yu. Ketkov, Dr. Gennady V. Markin, Sheng Y. Tzeng and Prof. Dr. Wen B. Tzeng

      Article first published online: 28 JAN 2016 | DOI: 10.1002/chem.201505039

      Thumbnail image of graphical abstract

      Our mutual influence: Mass-analyzed threshold ionization spectra of the chromium bisarene complexes bearing a toluene or biphenyl ligand reveal accurate contributions of a single methyl or phenyl group to changes in the ionization energy. Unprecedented resolution of the spectra provides new insights into the mutual influence of substituents in sandwich compounds.

  51. Full Papers

    1. Synthetic Methods | Hot Paper

      α-Amino Acid-Isosteric α-Amino Tetrazoles

      Ting Zhao, Katarzyna Kurpiewska, Justyna Kalinowska-Tłuścik, Eberhardt Herdtweck and Prof. Dr. Alexander Dömling

      Article first published online: 28 JAN 2016 | DOI: 10.1002/chem.201504520

      Thumbnail image of graphical abstract

      The good, the bad, and the Ugi: 20 natural proteinogenic and 4 other α-amino acid-isosteric α-amino tetrazoles have been synthesized under benign conditions according to a concise and efficient isocyanide-based multicomponent synthetic route. Several previously unknown ones are firstly synthesized and reported.

    2. Synthesis Design

      A New, Simple and Versatile Strategy for the Synthesis of Short Segments of Zigzag-Type Carbon Nanotubes

      Dr. Etienne André, Dr. Baptiste Boutonnet, Pauline Charles, Dr. Cyril Martini, Dr. Juan-Manuel Aguiar-Hualde, Dr. Sylvain Latil, Vincent Guérineau, Karim Hammad, Dr. Priyanka Ray, Dr. Régis Guillot and Dr. Vincent Huc

      Article first published online: 27 JAN 2016 | DOI: 10.1002/chem.201503693

      Thumbnail image of graphical abstract

      Cone-shaped scaffolds: A simple approach is described for the synthesis of short segments of zigzag carbon nanotubes. A calix[4]arene locked in the cone conformation is used as a scaffold for the construction of diameter-defined cyclo(m-phenylene), that is, a short segment of a (12,0) zigzag carbon nanotube (see figure).

    3. Peptide Synthesis

      Synthesis of Peptides by Silver-Promoted Coupling of Carboxylates and Thioamides: Mechanistic Insight from Computational Studies

      Prof. Craig A. Hutton, Jing Shang and Prof. Uta Wille

      Article first published online: 27 JAN 2016 | DOI: 10.1002/chem.201503753

      Thumbnail image of graphical abstract

      Peptide silver bullet: The mechanism of the N[RIGHTWARDS ARROW]C direction peptide synthesis through silver-promoted coupling of N-protected amino acids with thioacetylated amino esters is explored by using density functional theory (see scheme). The key step is the rearrangement of the intermediate isoimide to an imide through a concerted pericyclic [1,3]-acyl shift (O–sp2N 1,3-acyl migration).

    4. Ion–Molecule Reactions

      Capturing Transient Endoperoxide in the Singlet Oxygen Oxidation of Guanine

      Wenchao Lu and Prof. Jianbo Liu

      Article first published online: 27 JAN 2016 | DOI: 10.1002/chem.201504140

      Thumbnail image of graphical abstract

      Tracing DNA damage: Transient endoperoxide, which initiates the singlet O2 induced lesion of the guanine base of DNA, can be captured in gas-phase ion–molecule collision mass spectrometry (see figure). Experiments, corroborated by results from kinetic modelling and dynamics simulations, provide information about early-stage dynamics of guanine oxidation that is missing from conventional condensed-phase studies.

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