Chemistry - A European Journal

Cover image for Vol. 22 Issue 23

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

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  1. 1 - 100
  2. 101 - 163
  1. Full Papers

    1. Synthetic Methods | Hot Paper

      Direct Metal-Free Entry to Aminocyclobutenes or Aminocyclobutenols from Ynamides: Synthetic Applications

      Prof. Dr. Benito Alcaide, Prof. Dr. Pedro Almendros and Carlos Lázaro-Milla

      Version of Record online: 27 MAY 2016 | DOI: 10.1002/chem.201601044

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      Bis(triflyl)aminocyclobutenes, 2-amino-3-(triflyl)cyclobut-2-enols, or aminocyclobutenyl ethers from ynamides are prepared by a regioselective [2+2] cycloaddition or a cyclization/hydroxylation (hydroalkoxylation) sequence. These functionalized aminocyclobutenes are coverted into α-amino-β,γ-unsaturated ketones or 3-(triflyl)buta-1,3-dien-2-amines through 4 π-electrocyclic ring-opening reactions.

    2. Organocatalysis

      Aniline-Promoted Cyclization–Replacement Cascade Reactions of 2-Hydroxycinnamaldehydes with Various Carbonic Nucleophiles through In Situ Formed N,O-Acetals

      Chenguang Yu, He Huang, Xiangmin Li, Prof. Dr. Yueteng Zhang, Hao Li and Prof. Dr. Wei Wang

      Version of Record online: 27 MAY 2016 | DOI: 10.1002/chem.201601112

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      Cascade catalysis: New reactivity of N,O-acetals has been harnessed in an aminocatalytic cascade fashion for the efficient synthesis of 2-substituted 2H-chromenes.

  2. Communications

    1. Alkylation

      Manganese-Mediated C−H Alkylation of Unbiased Arenes Using Alkylboronic Acids

      Dr. Susana Castro, Juan J. Fernández, Prof. Dr. Francisco J. Fañanás, Dr. Rubén Vicente and Prof. Félix Rodríguez

      Version of Record online: 27 MAY 2016 | DOI: 10.1002/chem.201601482

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      The alkylation of simple arenes, usually performed by the traditional Friedel–Crafts reaction, may also be achieved by an alternative and competitive method involving alkylboronic acids as alkylating reagents and a manganese(III) salt as promoter (see scheme).

  3. Full Papers

    1. Computational Chemistry

      The Origin of Anti-Markovnikov Regioselectivity in Alkene Hydroamination Reactions Catalyzed by [Rh(DPEphos)]+

      Almudena Couce-Rios, Prof. Dr. Agustí Lledós and Dr. Gregori Ujaque

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/chem.201504645

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      Crossing paths: The reaction mechanism for intermolecular hydroamination of alkenes catalyzed by [Rh(DPEphos)]+ complex was analyzed by means of DFT calculations (see scheme). Hydroamination (alkene vs. amine activation routes) as well as oxidative amination pathways were analyzed.

    2. Drug Delivery

      Supramolecular Gels by Design: Towards the Development of Topical Gels for Self-Delivery Application

      Rumana Parveen and Prof. Dr. Parthasarathi Dastidar

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/chem.201600105

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      Anti-inflammatory gel: A supramolecular synthon approach has been adopted to generate a series of simple organic salts of ibuprofen. These are capable of forming topical gels, which proved to be useful both in vitro and in vivo to treat skin inflammation.

    3. Quantum Chemistry

      Reaction Mechanism of Mycobacterium Tuberculosis Glutamine Synthetase Using Quantum Mechanics/Molecular Mechanics Calculations

      Dr. Cátia Moreira, Prof. Maria J. Ramos and Prof. Pedro Alexandrino Fernandes

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/chem.201600305

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      The way mtGS works: The reaction mechanism for the conversion of glutamate into glutamine catalyzed by glutamine synthetase of pathogen mycobacterium tuberculosis (mtGS) was unraveled with atomistic detail, by employing computational quantum mechanics/molecular mechanics (QM/MM) methodology (model represented in figure).

    4. Host–Guest Chemistry | Hot Paper

      Aza-Bambusurils En Route to Anion Transporters

      Dr. Mandeep Singh, Ephrath Solel, Prof. Ehud Keinan and Dr. Ofer Reany

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/chem.201600343

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      En route to anion transporters: The solid-state structure confirms the simultaneous accommodation of three anions—two triflates and a bromide—linearly positioned along the main symmetry axis of semiaza-bambus[6]uril.

    5. Catalyst Design

      Computational Design of Iron Diphosphine Complexes with Pendant Amines for Hydrogenation of CO2 to Methanol: A Mimic of [NiFe] Hydrogenase

      Xiangyang Chen, Dr. Yuanyuan Jing and Prof. Dr. Xinzheng Yang

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/chem.201600764

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      Inspired by Nature: Density functional theory calculations indicate that a computationally designed diphosphine iron complex with pendant amine groups, namely, [PtBu2NtBu2)Fe(CN)2CO], is a promising candidate to catalyze the formation of methanol from CO2 and H2 with a total free energy barrier of 28.4 kcal mol−1 in aqueous solution (see scheme).

    6. Synthesis Design

      α,β-Double Electrophilic Addition of Allene-1,3-Dicarboxylic Esters for the Construction of Polysubstituted Furans by KI/tert-Butyl Hydroperoxide (TBHP)-Promoted Oxidative Annulation

      Hong-Liang Li, Yu Wang, Pei-Pei Sun, Prof. Dr. Xiaoyan Luo, Prof. Dr. Zhenlu Shen and Prof. Dr. Wei-Ping Deng

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/chem.201600771

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      Ring formation: An unprecedented KI/tert-butyl hydroperoxide (TBHP)-promoted tandem Michael addition/oxidative annulation of allene-1,3-dicarboxylic esters and 1,3-dicarbonyl compounds has been developed (see scheme). This provides a new, facile, and transition-metal-free synthetic approach to polysubstituted furans in moderate to excellent yields.

    7. Hydrogen Bonds | Hot Paper

      Charged versus Neutral Hydrogen-Bonded Complexes: Is There a Difference in the Nature of the Hydrogen Bonds?

      Prof. Ibon Alkorta, Dr. Ignasi Mata, Prof. Elies Molins and Prof. Enrique Espinosa

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/chem.201600788

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      Different but comparable: Charged and neutral hydrogen-bonded complexes have been investigated with regard to the nature of the formed hydrogen bonds. By applying different DFT methods no significant differences between the compared systems were found.

    8. Reaction Mechanisms

      Mechanism and Selectivity of RuII- and RhIII-Catalyzed Oxidative Spiroannulation of Naphthols and Phenols with Alkynes through a C−H Activation/Dearomatization Strategy

      Mei Zhang and Prof. Dr. Genping Huang

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/chem.201600884

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      An unusual metallacyclopropene (see scheme) was identified by DFT calculations as a key intermediate for the ruthenium- and rhodium-catalyzed oxidative spiroannulation of naphthols and phenols with alkynes. The subsequent C−C coupling between the carbene carbon atom and the carbon atom of the 2-naphthol/phenol ring leads to the formation of the unexpected dearomatized products.

  4. Communications

    1. Covalent Organic Frameworks

      Sophisticated Design of Covalent Organic Frameworks with Controllable Bimetallic Docking for a Cascade Reaction

      Dr. Wenguang Leng, Yongsheng Peng, Jianqiang Zhang, Dr. Hui Lu, Dr. Xiao Feng, Dr. Rile Ge, Dr. Bin Dong, Prof. Bo Wang, Prof. Xiangping Hu and Prof. Yanan Gao

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/chem.201601334

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      All in one! A series of two-dimensional covalent organic frameworks (COFs) containing two different types of nitrogen ligands with controllable contents have been designed and synthesized. The selective coordination of the two nitrogen ligands to two metal complexes, chloro(1,5-cyclooctadiene)rhodium(I) (Rh(COD)Cl) and palladium(II) acetate (Pd(OAc)2), has been realized. The bimetallically docked COFs showed excellent catalytic activity in a one-pot addition–oxidation cascade reaction (see scheme).

  5. Full Papers

    1. Supramolecular Chemistry

      An Easily Accessible Self-Healing Transparent Film Based on a 2D Supramolecular Network of Hydrogen-Bonding Interactions between Polymeric Chains

      Dr. Nabarun Roy, Dr. Željko Tomović, Prof. Eric Buhler and Prof. Jean-Marie Lehn

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/chem.201601378

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      Healing bonds: A self-healing covalent polymer, presenting an extensive array of hydrogen-bonding sites based on the combination of urea, urethane, and bis-acyl-hydrazine units is described (see scheme).

  6. Communications

    1. Supramolecular Chemistry

      Structural Changes of a Doubly Spin-Labeled Chemically Driven Molecular Shuttle Probed by PELDOR Spectroscopy

      Dr. Paola Franchi, Valentina Bleve, Prof. Dr. Elisabetta Mezzina, Christian Schäfer, Giulio Ragazzon, Dr. Marco Albertini, Prof. Donatella Carbonera, Prof. Dr. Alberto Credi, Prof. Marilena Di Valentin and Prof. Marco Lucarini

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/chem.201601407

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      PELDOR conquers: Pulsed electron–electron double resonance (PELDOR) spectroscopy was employed to monitor the geometrical changes arising upon chemical switching of a spin-labelled [2]rotaxane. The system behaves as an acid–base controlled molecular shuttle.

  7. Full Papers

    1. Metallocenes | Very Important Paper

      Multiple and Highly Selective Alkyne–Isonitrile C−C and C−N Couplings at Group 4 Metallocenes

      Dr. Kai Altenburger, Dr. Perdita Arndt, Dr. Lisanne Becker, Dr. Fabian Reiß, Dr. Vladimir V. Burlakov, Dr. Anke Spannenberg, Dr. Wolfgang Baumann and Prof. Dr. Uwe Rosenthal

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/chem.201601465

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      Selective but strange: The reactions of titano-, zircono- and hafnocene alkyne complexes with 2-xylyl isonitrile afford enamine complexes, aza-metallacycloallenes, and/or fused heterometallacycles, depending on the metal, the Cp′ ligand, and the stoichiometry applied. The alkyne always takes part in the coupling reactions. Furthermore, the metallocene is successfully expelled from the tricyclic complex to yield a highly functionalized pyrrole.

  8. Communications

    1. Synthetic Methods | Hot Paper

      Practical Stannylation of Allyl Acetates Catalyzed by Nickel with Bu3SnOMe

      Prof. Dr. Kimihiro Komeyama, Yuuhei Itai and Prof. Dr. Ken Takaki

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/chem.201601515

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      A simple but unique allylic stannylation of allyl acetates has been established by using nickel catalysts with Bu3SnOMe. Compared with the traditional stannylation, the present transformation features mild conditions, broad substrate scope, high regio- and diastereoselectivity, and gram-scale productivity (see scheme).

  9. Cover Pictures

    1. You have free access to this content
      Two-Dimensional Ketone-Driven Metal–Organic Coordination on Cu(111)

      Dr. Ada Della Pia, Dr. Massimo Riello, James Lawrence, Dr. Daphne Stassen, Prof. Tim S. Jones, Prof. Davide Bonifazi, Prof. Alessandro De Vita and Prof. Giovanni Costantini

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/chem.201602142

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      The pyrene 4,5,9,10-tetraone (PTO) molecule spontaneously forms two-dimensional metal–organic nanostructures with atoms from the substrate when deposited on a Cu(111) surface or with iron atoms if Fe is co-deposited with PTO. The nanostructures are stabilized by the coordination of individual metallic atoms by the molecule's strongly electronegative ketone moieties. The driving force for the substitution of Cu with Fe in the metal–organic complexes is determined by the relative strengths of the ketone–metal bond. More information can be found in the Full Paper by D. Bonifazi, A. De Vita, and G. Costantini et al. (DOI: 10.1002/chem.201600368).

    2. You have free access to this content
      Zinc Porphyrin Metal-Center Exchange at the Solid–Liquid Interface

      Matthias Franke, Florencia Marchini, Prof. Dr. Norbert Jux, Prof. Dr. Hans-Peter Steinrück, Dr. Ole Lytken and Prof. Dr. Federico J. Williams

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/chem.201602145

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      Porphyrin demetalation and metal-center exchange were investigated at the solid–liquid interface by exposing adsorbed zinc tetraphenylporphyrin on Au(111) to aqueous solutions. Metal-center exchange with copper ions at neutral pH took place rapidly, but demetalation under acidic conditions was not observed. This difference to liquid-phase chemistry is explained by the surface acting as a ligand for the zinc ion. More information can be found in the Full Paper by O. Lytken, F. J. Williams et al. (DOI: 10.1002/chem.201600634).

  10. Cover Profiles

    1. Hollow Gold Cages and Their Topological Relationship to Dual Fullerenes

      Lukas Trombach, Sergio Rampino, Lai-Sheng Wang and Prof. Peter Schwerdtfeger

      Version of Record online: 25 MAY 2016 | DOI: 10.1002/chem.201602148

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      L'art pour l'art, et la science pour la sciencethere is so much exciting and interesting new science yet to be discovered…” Read more about the story behind the cover in the Cover Profile and about the research itself on page ▪▪ ff. (DOI: 10.1002/chem.201601239).

  11. Full Papers

    1. Sensors

      A 1,3-Capped Calix[4] Conjugate Possessing an Amine Moiety as an Anion Receptor: Reversible Anion Sensing Detected by Spectroscopy and Characterization of the Supramolecular Features by Microscopy

      Dr. Anita Nehra, Deepthi S. Yarramala and Prof. Chebrolu Pulla Rao

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/chem.201600609

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      Changing behavior: A phenylenediamine-capped conjugate of calix[4]arene (Lamino) was synthesized by reducing its precursor, Limino, with sodium borohydride in methanol. The Lamino sample binds to anions due to the more flexible and bent conformation of the capped aminophenolic binding core (see figure).

    2. Medicinal Chemistry

      Multifaceted Studies of the DNA Interactions and In Vitro Cytotoxicity of Anticancer Polyaromatic Platinum(II) Complexes

      Benjamin J. Pages, Dr. Jennette Sakoff, Dr. Jayne Gilbert, Prof. Alison Rodger, Dr. Nikola P. Chmel, Nykola C. Jones, Dr. Sharon M. Kelly, Dale L. Ang and Prof. Janice R. Aldrich-Wright

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/chem.201601221

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      A frame of bind: DNA binding behaviour of six polyaromatic platinum anticancer complexes has been studied using six biophysical methods (linear dichroism pictured), resulting in a comparison of the merits of each technique and the establishment of trends in DNA affinity in relation to complex structure. In vitro cytotoxicity in a panel of human cells was determined, revealing submicromolar activity in Du145 and SJ-G2 cells. Correlations between activity and DNA affinity were determined.

  12. Communications

    1. Gold Catalysis

      Gold-Catalyzed Reaction of ortho-Alkynylarylaldehydes with Conjugated Dienes: An Efficient Access to Highly Strained Tetracyclic Bridgehead Olefins

      Dr. Ziping Cao, Hongbo Zhu, Dr. Xin Meng, Laijin Tian, Xuejun Sun, Guang Chen and Prof. Jinmao You

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/chem.201601430

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      Walking a tight bridge: An unprecedented access to strained tetracyclic bridgehead alkenes by reaction of easily accessible ortho-alkynylarylaldehydes with conjugated dienes is described. The process is proposed to involve a chemo- and stereo-selective, gold-catalyzed, tandem intermolecular [3+2] cycloaddition/Prins-type ring-closing reaction that generates structural complexity in a straightforward manner.

  13. Full Papers

    1. Materials Science

      Efficient White-Light Generation from Ionically Self-Assembled Triply-Fluorescent Organic Nanoparticles

      Dr. Susmita Das, Tanay Debnath, Amrita Basu, Dr. Deepanwita Ghosh, Prof. Abhijit Kumar Das, Dr. Gary A. Baker and Prof. Amitava Patra

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/chem.201502339

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      The light fantastic: Intramolecular proton transfer and frustrated energy transfer induced intense white-light emission from a triply fluorescent organic nanoparticle (see figure).

    2. Self-Assembly

      Self-Assembled Fibers Containing Stable Organic Radical Moieties: Alignment and Magnetic Properties in Liquid Crystals

      Hiroki Eimura, Yoshikazu Umeta, Prof. Dr. Hiroko Tokoro, Prof. Dr. Masafumi Yoshio, Prof. Dr. Shin-ichi Ohkoshi and Prof. Dr. Takashi Kato

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/chem.201505213

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      Liquid–crystalline physical gels of a stable organic radical gelator have been developed. Magnetic field alignment leads to unidirectional formation of fibrous aggregates of the radical gelators in oriented liquid crystals. Magnetic measurements have shown that fiber formation of the organic radical gelators induces antiferromagnetic interaction and the macroscopic alignment structures of fibrils have no effect on the magnetic properties (see figure).

    3. Catalytic Nanosheets

      Enhanced Catalytic Activity in Liquid-Exfoliated FeOCl Nanosheets as a Fenton-Like Catalyst

      Jian Zhang, Prof. Xiu-Ling Jiao, Dr. Yu-Guo Xia, Fang-Fang Liu, Ying-Ping Pang, Xin-Fu Zhao and Prof. Dai-Rong Chen

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/chem.201600172

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      Fenton nanosheets: Few-layer FeOCl nanosheets are successfully prepared by a liquid-phase exfoliation method. The nanosheets show outstanding properties in the catalytic degradation of phenol in water at room temperature, under neutral pH conditions, and with sunlight compared with FeOCl plates (see figure).

    4. Structure–Activity Relationships

      Synthesis of Firefly Luciferin Analogues and Evaluation of the Luminescent Properties

      Shuji Ioka, Dr. Tsuyoshi Saitoh, Dr. Satoshi Iwano, Prof. Dr. Koji Suzuki, Dr. Shojiro A. Maki, Prof. Dr. Atsushi Miyawaki, Prof. Dr. Masaya Imoto and Prof. Dr. Shigeru Nishiyama

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/chem.201600278

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      All aglow: Luciferin derivatives possessing acyclic amino acid and heterocyclic substituents were synthesized. All synthetic derivatives displayed chemiluminescence, but only d-carboluciferin showed 0.5 % bioluminescence (BL) activity compared with that of firefly luciferin. d-Carboluciferin differed from firefly luciferin in that decay of its BL in live mice was slower than that of the natural luciferin (see figure).

    5. Imaging Agents

      New Red-Emitting Tetrazine-Phenoxazine Fluorogenic Labels for Live-Cell Intracellular Bioorthogonal Labeling Schemes

      Gergely Knorr, Eszter Kozma, Dr. András Herner, Dr. Edward A. Lemke and Dr. Péter Kele

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/chem.201600590

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      Put a tag on it: The synthesis and bioorthogonal labeling potential of a set of tetrazine-based fluorogenic dyes suitable for intracellular labeling of proteins in live cells is presented (see figure). The red excitability and emission properties ensure minimal autofluorescence, while the through-bond energy-transfer-based fluorogenicity reduces nonspecific background fluorescence of unreacted dyes.

    6. Metallaboranes

      New Trinuclear Complexes of Group 6, 8, and 9 Metals with a Triply Bridging Borylene Ligand

      K. Yuvaraj, Moulika Bhattacharyya, Rini Prakash, V. Ramkumar and Prof. Dr. Sundargopal Ghosh

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/chem.201600637

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      Building boron bridges: The thermolysis of half-sandwich complexes of nido-[(Cp*M)2B3H7] (M=Rh, RuH; Cp*=η5-C5Me5) with a group 6 metal carbonyl [M(CO)5thf] (M=Cr, Mo, W) led to the formation of a heterotrimetallic complexes with a triply bridging borylene ligand (see figure).

  14. Communications

    1. Hybrid Micromotors

      Autonomously Propelled Motors for Value-Added Product Synthesis and Purification

      Dr. Sarvesh K. Srivastava and Prof. Dr. Oliver G. Schmidt

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/chem.201600923

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      Get your motor running: A proof-of-concept for self-propelling motors for product synthesis and separation is presented. The hybrid motor consists of a NaBH4 granule for the reduction of vanillin and also as a solid-state fuel and a capping graphene–polymer composite as a hydrophobic matrix to attract and separate the reaction product, vanillyl alcohol. The autonomously propelled motors were fabricated at a length scale down to 400 μm.

    2. Peptide Therapeutics

      Effective Inhibition of Cellular ROS Production by MXCXXC-Type Peptides: Potential Therapeutic Applications in Copper-Homeostasis Disorders

      Dr. Michal S. Shoshan and Prof. Edit Y. Tshuva

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/chem.201601017

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      Fighting Wilson's disease: Peptides with sequences derived from metallochaperone binding sites were analyzed for their inhibitory reactivity towards cellular ROS (reactive oxygen species) formation. A leading peptide exhibited particularly high efficiency when compared to known drugs for Wilson's disease. This peptide also showed no toxicity towards human colon-cancer cells, corroborating its high medicinal potential.

  15. Full Papers

    1. Anion Receptors

      Straightforward and Controlled Shape Access to Efficient Macrocyclic Imidazolylboronium Anion Receptors

      Momar Toure, Prof. Dr. Laurence Charles, Christophe Chendo, Prof. Dr. Stéphane Viel, Dr. Olivier Chuzel and Dr. Jean-Luc Parrain

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/chem.201601174

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      Plus to see minus: A straightforward and efficient synthesis of highly effective bis-cationic macrocyclic imidazolylboronium anion receptors (see figure) is depicted in this study. The crucial boronium part governed the self-assembly and the specific electronic property of this novel anion receptor. The bis-cationic nature of the macrocycle allowed trapped anions to be detected directly by using positive mass spectrometry.

  16. Communications

    1. Carbon Dioxide Reduction

      A Monolithically Integrated Gallium Nitride Nanowire/Silicon Solar Cell Photocathode for Selective Carbon Dioxide Reduction to Methane

      Dr. Yichen Wang, Shizhao Fan, Bandar AlOtaibi, Yongjie Wang, Dr. Lu Li and Prof. Zetian Mi

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/chem.201601642

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      Yes we GaN: A silicon solar cell photocathode with a GaN nanowire for the photo-reduction of CO2 is reported. Such a photocathode offers the absorption of a large part of the solar spectrum and highly efficient carrier extraction. With the incorporation of Cu as the co-catalyst, the devices exhibit a Faradaic efficiency of about 19 % for the 8e photoreduction to CH4.

    2. Molecular Dynamics

      Understanding Amyloid-β Oligomerization at the Molecular Level: The Role of the Fibril Surface

      Dr. Bogdan Barz and Dr. Birgit Strodel

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/chem.201601701

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      Amyloid β-peptide oligomers play a crucial role in Alzheimer's disease. The production of highly toxic Aβ oligomers is catalyzed by amyloid fibrils. Molecular dynamics simulations reveal that the exposed hydrophobicity of the fibril surface causes substantial structural changes in Aβ and modifies its aggregation behavior.

    3. Asymmetric Cycloadditions

      Asymmetric Organocatalytic Stepwise [2+2] Entry to Tetra-Substituted Heterodimeric and Homochiral Cyclobutanes

      Alex J. Nielsen, Dr. Hilary A. Jenkins and Dr. James McNulty

      Version of Record online: 24 MAY 2016 | DOI: 10.1002/chem.201601842

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      Head-to-tail approach: An asymmetric synthesis of tetra-substituted cyclobutanes involving an organocatalytic, stepwise [2+2]-cycloaddition is described. The secondary-amine-catalyzed method allows for the hetero-dimerization of two different cinnamic acid-derived sub-units, opening a novel one-step assembly to densely functionalized, head-to-tail coupled dimeric cyclobutanes in high enantiomeric excess. A series of selective synthetic interconversions in these sensitive cycloadducts is also described.

    4. Nanotechnology | Hot Paper

      Ultrathin Coating of Confined Pt Nanocatalysts by Atomic Layer Deposition for Enhanced Catalytic Performance in Hydrogenation Reactions

      Meihua Wang, Dr. Zhe Gao, Dr. Bin Zhang, Huimin Yang, Prof. Yan Qiao, Shuai Chen, Huibin Ge, Jiankang Zhang and Prof. Yong Qin

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/chem.201601039

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      Go nano! ALD was applied to deposit ultrathin Al2O3 coats on Pt nanoparticles that are confined in Al2O3 nanotubes. Compared with the confined catalysts without the ultrathin coats, the ultrathin-coated samples possess more Pt–Al2O3 interfacial sites. The maximized interfaces significantly improve the activities and the protecting nanotubes retain the stabilities for hydrogenation reactions of 4-nitrophenol (see figure).

  17. Cover Pictures

    1. You have free access to this content
      Active Esters as Pseudostoppers for Slippage Synthesis of [2]Pseudorotaxane Building Blocks: A Straightforward Route to Multi-Interlocked Molecular Machines

      Dr. Thibaut Legigan, Benjamin Riss-Yaw, Dr. Caroline Clavel and Dr. Frédéric Coutrot

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/chem.201601890

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      Synthesizing a palindromic [3]rotaxane molecular machines……using [2]rotaxane building-blocks. The picture represents the famous intriguing “Rotas or Sator Square”, i.e. a word square that contains a Latin palindrome that can be built from stone blocks. The sentence, which can be read in all directions, combines the words “rotas”, meaning wheel, and “opera” for task. A chemical analogy can be found with symmetrical rotaxane architectures, in which the motion of a chemical wheel can be linked to work. In their article, F. Coutrot et al. describe the synthesis of a pH-sensitive [3]rotaxane palindromic molecular machine from novel appealing isolable and storable activated [2]rotaxane building-blocks. More information can be found in the Full Paper by F. Coutrot et al. (DOI: 10.1002/chem.201601286).

  18. Full Papers

    1. Enzyme Inhibition | Hot Paper

      Phosphono Bisbenzguanidines as Irreversible Dipeptidomimetic Inhibitors and Activity-Based Probes of Matriptase-2

      Daniela Häußler, Martin Mangold, Norbert Furtmann, Dr. Annett Braune, Prof. Dr. Michael Blaut, Prof. Dr. Jürgen Bajorath, Dr. Marit Stirnberg and Prof. Dr. Michael Gütschow

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/chem.201600206

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      A triple hold on matriptase-2: Inhibition of matriptase-2 is considered as an attractive strategy for the treatment of iron-overload diseases. Nine peptidomimetic inactivators were synthesized with a phosphonate warhead and two benzguanidine moieties as arginine mimetics (see scheme). Five of these were characterized as irreversible inhibitors of matriptase-2. Insertion of a coumarin label generated the first activity-based fluorescent probe for matriptase-2.

  19. Cover Profiles

    1. Ultrathin Coating of Confined Pt Nanocatalysts by Atomic Layer Deposition for Enhanced Catalytic Performance in Hydrogenation Reactions

      Meihua Wang, Dr. Zhe Gao, Dr. Bin Zhang, Huimin Yang, Prof. Yan Qiao, Shuai Chen, Huibin Ge, Jiankang Zhang and Prof. Yong Qin

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/chem.201601892

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      The method of coating the confined catalysts can be extended to other catalytic systems in which the metal-support interfaces have a strong effect on the catalytic performance.” Read more about the story behind the cover in the Cover Profile and about the research itself on page ▪▪ ff. (DOI: 10.1002/chem.201601039).

  20. Cover Pictures

    1. You have free access to this content
      Synergistic Effects of Metals in a Promising RuII−PtII Assembly for a Combined Anticancer Approach: Theoretical Exploration of the Photophysical Properties

      Dr. Marta E. Alberto, Prof. Nino Russo and Prof. Dr. Carlo Adamo

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/chem.201602147

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      United against cancer: RuII−PtII complexes are a class of bioactive molecules that are of interest as anticancer agents. They are obtained by combining a light-absorber chromophore with a cisplatin-like unit. The PtII moiety tunes the photophysical properties of the RuII chromophore, ensuring efficient singlet oxygen generation and enhancing the potential efficiency of the conjugate in photodynamic therapy, whereas the RuII chromophore promotes an alternative activation mechanism of the PtII ligand before reaching the biological target, through low-energy light-induced photolabilization of the Pt−Cl bond promoted, upon irradiation, by a triplet metal-to-ligand charge transfer state. More information can be found in the Full Paper by M. E. Alberto et al. on page ▪▪ ff. (DOI: 10.1002/chem.201601089).

    2. You have free access to this content
      Synthetically Tuning the 2-Position of Halogenated Quinolines: Optimizing Antibacterial and Biofilm Eradication Activities via Alkylation and Reductive Amination Pathways

      Akash Basak, Yasmeen Abouelhassan, Verrill M. Norwood IV, Dr. Fang Bai, Minh Thu Nguyen, Prof. Shouguang Jin and Prof. Robert W. Huigens III

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/chem.201602069

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      The 2-position of the halogenated quinoline (HQ) scaffold can be dramatically tuned through diverse and practical synthetic pathways, including reductive amination and alkylation reactions. New HQs discovered during these investigations potently eradicate methicillin-resistant Staphylococcus aureus (MRSA), methicillin-resistant Staphylococcus epidermidis (MRSE) and vancomycin-resistant Enterococcus faecium (VRE) biofilms, which display high levels of tolerance towards conventional antibiotic therapies. The background image is reproduced with permission and copyright© of the British Editorial Society of Bone and Joint Surgery (Bone Joint J. 2013, 95B, 678–682; Figure 2 b). More information can be found in the Full Paper by R. W. Huigens III et al. (DOI: 10.1002/chem.201600926).

    3. You have free access to this content
      Ultrathin Coating of Confined Pt Nanocatalysts by Atomic Layer Deposition for Enhanced Catalytic Performance in Hydrogenation Reactions

      Meihua Wang, Dr. Zhe Gao, Dr. Bin Zhang, Huimin Yang, Prof. Yan Qiao, Shuai Chen, Huibin Ge, Jiankang Zhang and Prof. Yong Qin

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/chem.201601887

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      A strategy to maximize the metal-oxide interfaces is proposed by coating confined nanoparticles with an ultrathin oxide layer. The main features of the designed catalyst are: Al2O3 nanotubes, confined Pt nanoparticles, and ultrathin Al2O3 coats. These features are represented in the cover-page graphic. The Pt nanoparticles (yellow ball) were partially embedded in the internal wall of the Al2O3 nanotubes (gray cylindrical tube) and uniformly coated by the ultrathin Al2O3 layer (gray ball). More information can be found in the Communication by Z. Gao, Y. Qin et al. (DOI: 10.1002/chem.201601039).

    4. You have free access to this content
      Phosphono Bisbenzguanidines as Irreversible Dipeptidomimetic Inhibitors and Activity-Based Probes of Matriptase-2

      Daniela Häußler, Martin Mangold, Norbert Furtmann, Dr. Annett Braune, Prof. Dr. Michael Blaut, Prof. Dr. Jürgen Bajorath, Dr. Marit Stirnberg and Prof. Dr. Michael Gütschow

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/chem.201601295

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      Phosphono bisbenzguanidines as dipeptidomimetic inactivators for matriptase-2 were discovered. Inhibition of this enzyme is one strategy for the treatment of iron-overload diseases. Synthetic routes to new inactivators were developed. The irreversible inhibition was kinetically characterized and the binding mode was supported by docking analysis. Based on this chemotype, a fluorescent probe was designed and synthesized. Finally, by applying the first activity-based probe for matriptase-2, detection of the target was demonstrated. More information can be found in the Full Paper by M. Gütschow, et al. (DOI: 10.1002/chem.201600206).

    5. You have free access to this content
      Hollow Gold Cages and Their Topological Relationship to Dual Fullerenes

      Lukas Trombach, Sergio Rampino, Lai-Sheng Wang and Prof. Peter Schwerdtfeger

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/chem.201602144

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      Golden dual fullerenes are hollow gold cages that are triangulations of a sphere and topologically isomorph to the well know fullerenes according to Euler's polyhedral formula. This also relates the (111) fcc gold layer to the graphene surface, the gold nanowires to the carbon nanotubes, and the Mackay icosahedra well known in cluster growth simulations to the halma transforms of the fullerene C20. In the picture C60 and its golden dual Au32 are shown with the background of Auckland's skyline. More information can be found in the Full Paper by P. Schwerdtfeger et al. (DOI: 10.1002/chem.201601239).

    6. You have free access to this content
      Effects of Aromatic Fluorine Substitution on Protonated Neurotransmitters: The Case of 2-Phenylethylamine

      Markus Schütz, Aude Bouchet, Barbara Chiavarino, Maria Elisa Crestoni, Simonetta Fornarini and Otto Dopfer

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/chem.201601652

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      Fluorination of pharmaceutical compounds is a common tool to modulate their physiochemical properties. The large effects of site-specific aromatic fluorination of a protonated prototypical neurotransmitter (2-phenylethylamine) have accurately been determined by infrared spectroscopy and dispersion-corrected density functional theory calculations of ions isolated in the gas phase. The strengths of the various competing intramolecular noncovalent interactions (NH+⋅⋅⋅π, NH+⋅⋅⋅F) depend strongly on the fluorination site. Inset image of neurons courtesy of the National Institutes on Ageing/National Institutes of Health. More information can be found in the Full Paper by O. Dopfer et al. (DOI: 10.1002/chem.201600798).

  21. Full Papers

    1. Structure Elucidation | Hot Paper

      Effects of Aromatic Fluorine Substitution on Protonated Neurotransmitters: The Case of 2-Phenylethylamine

      M. Sc. Markus Schütz, Dr. Aude Bouchet, Prof. Barbara Chiavarino, Prof. Maria Elisa Crestoni, Prof. Simonetta Fornarini and Prof. Otto Dopfer

      Version of Record online: 23 MAY 2016 | DOI: 10.1002/chem.201600798

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      Fluorination makes the difference: The large effects of site-specific aromatic fluorination of a prototypical protonated neurotransmitter (2-phenylethylamine) have been determined by infrared spectroscopy and dispersion-corrected density functional theory calculations of ions isolated in the gas phase. The strengths of the various competing noncovalent interactions (NH+⋅⋅⋅π, NH+⋅⋅⋅F) depend strongly on the fluorination site (see figure).

  22. Concepts

    1. Olefin Metathesis

      Tandem Catalysis Utilizing Olefin Metathesis Reactions

      Grzegorz K. Zieliński and Prof. Dr. Karol Grela

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/chem.201505136

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      Pedal to the metal: Various examples of tandem catalysis involving olefin metathesis are discussed, with a view to illustrating some interesting synthetic concepts and showing their synthetic value. The differences between tandem processes and other types of one-pot transformation are stressed.

  23. Full Papers

    1. Supramolecular Chemistry | Hot Paper

      Dipolar Photosystems: Engineering Oriented Push–Pull Components into Double- and Triple-Channel Surface Architectures

      Dr. Altan Bolag, Dr. Naomi Sakai and Prof. Stefan Matile

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/chem.201600213

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      Oriented macrodipoles: Ordered multicomponent architectures were synthesized to explore dipolar photosystems. Whereas mixed stacking is unfavorable, the direction of parallel dipoles has surprisingly little effect on the photocurrent generation by double-channel photosystems. In triple-channel architectures, more significant optical gating is found upon direct irradiation of the oriented dipolar stacks between the stacks of donors and acceptors.

  24. Communications

    1. Difluoromethylation

      Computational SN2-Type Mechanism for the Difluoromethylation of Lithium Enolate with Fluoroform through Bimetallic C−F Bond Dual Activation

      Kazuya Honda, Dr. Travis V. Harris, Dr. Miho Hatanaka, Prof. Dr. Keiji Morokuma and Prof. Dr. Koichi Mikami

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/chem.201601090

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      A computational study on the direct difluoromethylation of lithium enolates with the artificial force induced reaction (AFIR) method was performed. The reaction proceeds through an SN2-like carbon–carbon bond-formation transition state involving a non-butterfly-shaped, bimetallic difluoromethylcarbenoid species (see scheme).

  25. Full Papers

    1. Natural Products | Very Important Paper

      A Two-Component Alkyne Metathesis Catalyst System with an Improved Substrate Scope and Functional Group Tolerance: Development and Applications to Natural Product Synthesis

      Sebastian Schaubach, Dr. Konrad Gebauer, Felix Ungeheuer, Dr. Laura Hoffmeister, Marina K. Ilg, Conny Wirtz and Prof. Alois Fürstner

      Version of Record online: 20 MAY 2016 | DOI: 10.1002/chem.201601163

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      Ill-defined but well-behaved: Although oligomeric in nature, alkyne metathesis catalysts formed in situ by mixing of a trisamido molybdenum alkylidyne complex and an appropriate trisilanol were found highly tolerant of sensitive functional groups and protic sites. This notion is witnessed by the total syntheses of the sesquiterpene lactone manshurolide, the immunosuppressive cyclodiyne ivorenolide A, as well as by studies toward the quinolizidine alkaloid lythrancepine I (see scheme).

    2. Fluorescence | Hot Paper

      Facile Preparation of Bright-Fluorescent Soft Materials from Small Organic Molecules

      Dr. Hang-Xing Wang, Ze Yang, Zhong-Guo Liu, Jia-Yun Wan, Juan Xiao and Prof. Hao-Li Zhang

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/chem.201600448

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      Bright side of soft materials: We report a facile approach for the preparation of a new fluorescent soft material, which relies on directly heating an aqueous mixture of citric acid and cysteine at low temperature in air (see figure).

    3. Cyclometalated Complexes

      Strongly Coupled Cyclometalated Ruthenium Triarylamine Chromophores as Sensitizers for DSSCs

      Christoph Kreitner, Andreas K. C. Mengel, Tae Kyung Lee, Woohyung Cho, Prof. Dr. Kookheon Char, Prof. Yong Soo Kang and Prof. Dr. Katja Heinze

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/chem.201601001

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      Anchor-functionalized cyclometalated bis(tridentate) ruthenium(II) triarylamine hybrids featuring mixed-valent states of varying resonance stabilization were employed in dye-sensitized solar cells in combination with different electrolytes. Together with cobalt-based electrolytes, the N-carbazole substituted dye surpasses the N719 dye.

  26. Cover Pictures

    1. You have free access to this content
      Host–Guest Binding-Site-Tunable Self-Assembly of Stimuli-Responsive Supramolecular Polymers

      Hao Yao, Miao Qi, Prof. Dr. Yuyang Liu and Prof. Dr. Wei Tian

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/chem.201602075

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      The β-cyclodextrin/azobenzene host–guest binding site has a pronounced effect on the morphology, size, dynamic self-assembly process, and controlled release function of two thermo- and photoresponsive Y-shaped supramolecular polymer self-assemblies. The binding-site-tunable self-assembly can be attributed to the positive cooperativity generated amongst adjacent binding sites on the surfaces of supramolecular polymer self-assemblies. More information can be found in the Full Paper by W. Tian et al. (DOI: 10.1002/chem.201601142).

  27. Communications

    1. Synthetic Methods

      You have full text access to this OnlineOpen article
      Catalyst-Driven Scaffold Diversity: Selective Synthesis of Spirocycles, Carbazoles and Quinolines from Indolyl Ynones

      Dr. John T. R. Liddon, Michael J. James, Aimee K. Clarke, Prof. Peter O'Brien, Prof. Richard J. K. Taylor and Dr. William P. Unsworth

      Version of Record online: 19 MAY 2016 | DOI: 10.1002/chem.201601836

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      Medicinally relevant spirocyclic indolenines, carbazoles and quinolines can each be directly synthesised selectively from common indolyl ynone starting materials by catalyst variation (see scheme). The high yielding, divergent reactions all proceed by an initial dearomatising spirocyclisation reaction to generate an intermediate vinyl–metal species, which then rearranges selectively by careful choice of catalyst and reaction conditions.

  28. Full Papers

    1. Reaction Mechanisms

      Silver(I)-Catalyzed Addition of Phenols to Alkyne Cobalt Cluster Stabilized Carbocations

      Dr. Carolina Valderas, Prof. Dr. Luis Casarrubios, Prof. Dr. Agusti Lledos, Dr. Manuel A. Ortuño, Dr. María C. de la Torre and Prof. Dr. Miguel A. Sierra

      Version of Record online: 17 MAY 2016 | DOI: 10.1002/chem.201600288

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      Making the unreactive react: Phenols can be used as nucleophilic partners in the Nicholas reaction by using either silver(I) or gold(I) catalysts (see figure). Neither additional additives nor cocatalysts are required and the formation of the corresponding phenol adducts occurs in excellent yields. In contrast, the “classical” Nicholas reaction with phenols is not possible.

    2. Total Synthesis | Hot Paper

      You have free access to this content
      Total Synthesis of Δ12-Prostaglandin J3: Evolution of Synthetic Strategies to a Streamlined Process

      Prof. Dr. K. C. Nicolaou, Dr. Kiran Kumar Pulukuri, Ruocheng Yu, Dr. Stephan Rigol, Dr. Philipp Heretsch, Dr. Charles I. Grove, Christopher R. H. Hale and Dr. Abdelatif ElMarrouni

      Version of Record online: 17 MAY 2016 | DOI: 10.1002/chem.201601449

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      Streamlining the synthesis of Δ12-prostaglandin J3 proceeded through improvements in the construction of both the key enone and aldehyde building blocks, exploration of the chemistry of the hitherto underutilized chiral lactone synthon, and a diastereoselective alkylation of a cyclopentenone intermediate. The described chemistry sets the stage for large-scale production of Δ12-prostaglandin J3 and designed analogues for further biological and pharmacological studies.

  29. Communications

    1. Cyclization

      Multicomponent Double Diels–Alder/Nazarov Tandem Cyclization of Symmetric Cross-Conjugated Diynones to Generate [6-5-6] Tricyclic Products

      Rachael A. Carmichael and Prof. Wesley A. Chalifoux

      Version of Record online: 17 MAY 2016 | DOI: 10.1002/chem.201601850

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      Sign o′ the diynones: The synthesis of [6-5-6]-tricyclic products has been achieved in an efficient one-pot multicomponent reaction starting from reactive cross-conjugated diynones and proceeding through a double Diels–Alder/Nazarov tandem reaction sequence.

    2. Porphyrinoids

      β-to-β 2,5-Pyrrolylene-Linked Cyclic Porphyrin Oligomers

      Yutao Rao, Jun Oh Kim, Woojae Kim, Guangming Zhong, Dr. Bangshao Yin, Dr. Mingbo Zhou, Prof. Dr. Hiroshi Shinokubo, Prof. Dr. Naoki Aratani, Dr. Takayuki Tanaka, Prof. Dr. Shubin Liu, Prof. Dr. Atsuhiro Osuka, Prof. Dr. Dongho Kim and Prof. Dr. Jianxin Song

      Version of Record online: 17 MAY 2016 | DOI: 10.1002/chem.201601306

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      Cyclic porphyrin oligomers, formed by β-to-β linking with 2,5-pyrrolylene, have been synthesized by Suzuki–Miyaura coupling of 2,5-diborylpyrrole and 3,7-dibromoporphyrin. The cyclic porphyrin oligomers (trimer shown in picture; N blue, Ni green) exhibit roughly coplanar structures, strong excitonic coupling, small electrochemical HOMO–LUMO gaps, and ultrafast excitation energy transfer between the neighboring porphyrins via the pyrrolylene bridge.

    3. Metallacycles

      Synthesis and DFT Study of a Diphenylsilanone-Bridged Dimolybdenum Complex

      Dr. M. Angeles Alvarez, Prof. Dr. M. Esther García, Dr. Daniel García-Vivó, Dr. Sonia Menéndez and Prof. Dr. Miguel A. Ruiz

      Version of Record online: 13 MAY 2016 | DOI: 10.1002/chem.201601598

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      Bridge of silanones: An unsaturated dimolybdenum complex with a bridging diphenylsilanone (Ph2SiO) ligand was prepared by oxidation of an intermediate silylene complex. X-ray data and DFT calculations indicate that the central Mo2SiO ring in this compound approaches the extreme description of a dimetallacyclosiloxane ring, with an oxygen electron lone pair also involved in bonding with the dimetal unit.

    4. Porous Monoliths

      Assembly of a Metal–Organic Framework into 3 D Hierarchical Porous Monoliths Using a Pickering High Internal Phase Emulsion Template

      He Zhu, Prof. Dr. Qi Zhang and Prof. Dr. Shiping Zhu

      Version of Record online: 13 MAY 2016 | DOI: 10.1002/chem.201600313

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      Do believe the HIPE: Pickering high internal phase emulsions (HIPEs) were stabilized solely by UiO-66 particles with up to 90 vol % internal phase. 3D hierarchical porous metal–organic framework monoliths were successfully prepared through this Pickering HIPE template.

  30. Full Papers

    1. CO Oxidation

      Multiple CO Oxidation Promoted by Au2 Dimers in Au2TiO4 Cluster Anions

      Dr. Xiao-Na Li, Dr. Zi-Yu Li, Hai-Fang Li and Prof. Dr. Sheng-Gui He

      Version of Record online: 13 MAY 2016 | DOI: 10.1002/chem.201600451

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      More the merrier: Time-of-flight mass spectrometry experiments and quantum chemistry calculations demonstrated that the Au2 dimer in Au2TiO4 clusters functions as a rather flexible electron reservoir to promote the dissociation of superoxide to peroxide and then to lattice oxygen species, which can be removed by reaction with three CO molecules consecutively (see figure).

  31. Communications

    1. C−H Functionalization

      Weak O-Assistance Outcompeting Strong N,N-Bidentate Directing Groups in Copper-Catalyzed C−H Chalcogenation

      Dr. Gianpiero Cera and Prof. Dr. Lutz Ackermann

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/chem.201601821

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      Weak over strong: Fully substituted 1,2,3-triazoles were accessed by C−H chalcogenation through weak O-assistance by overriding strong bidentate N,N-directing groups, which enabled robust C−H selenylations and C−H sulfenylations with ample substrate scope (see scheme).

  32. Full Papers

    1. Density Functional Calculations

      Double Pancake Versus Long Chalcogen–Chalcogen Bonds in Six-Membered C,N,S-Heterocycles

      Prof. Dr. Gebhard Haberhauer and Prof. Dr. Rolf Gleiter

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/chem.201601121

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      Bonding models: A new interpretation for the short distances between the rings in the dimers of six-membered C,N,S-heterocycles is given (see figure).

    2. Total Synthesis

      The Total Synthesis of Starfish Ganglioside GP3 Bearing a Unique Sialyl Glycan Architecture

      Kenta Goto, Maki Sawa, Dr. Hideki Tamai, Dr. Akihiro Imamura, Dr. Hiromune Ando, Dr. Hideharu Ishida and Dr. Makoto Kiso

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/chem.201600970

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      Sialic acids as the linchpin: The total synthesis of the largest echinodarmatous ganglioside, GP-3, is described. A highly reactive and stereoselective sialic acid donor with orthogonal protections led to the construction of sialic acid-embedded tetrasaccharide synthetic units. [4+4] convergent coupling followed by coupling with a glucosyl ceramide cassette and global deprotection successfully delivered the target compound.

    3. Asymmetric Total Synthesis of Heronamides A–C: Stereochemical Confirmation and Impact of Long-Range Stereochemical Communication on the Biological Activity

      Prof. Dr. Naoki Kanoh, Shunya Itoh, Kohei Fujita, Dr. Kohei Sakanishi, Ryosuke Sugiyama, Yuta Terajima, Prof. Dr. Yoshiharu Iwabuchi, Prof. Dr. Shinichi Nishimura and Prof. Dr. Hideaki Kakeya

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/chem.201600569

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      Long-distance communication matters: Asymmetric total synthesis of the originally proposed and revised structures of heronamide C, and nonenzymatic synthesis of heronamides A and B from heronamide C is described (see scheme). Investigation of the structure–activity relationship of synthetic and natural heronamides revealed the importance of both long-range stereochemical communication and the 20-membered macrolactam ring for the biological activity of these compounds.

    4. Sensors

      A Naphthalimide-Based Cd2+ Fluorescent Probe with Carbamoylmethyl Groups Working as Chelators and PET-Promoters under Neutral Conditions

      Dr. Koji Tsukamoto, Shota Shimabukuro, Dr. Miyuki Mabuchi and Prof. Dr. Hatsuo Maeda

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/chem.201600556

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      The PET set: A naphthalimide-based fluorescent probe has been designed for sensing Cd2+, and the probes applicable to practical use in water or biological samples have been developed. Comparison of various derivatives of the probe suggests that the sensing mechanism for Cd2+ occurs through photoinduced electron transfer (PET; see figure).

  33. Communications

    1. Cage Compounds

      Encapsulation of Formaldehyde and Hydrogen Cyanide in an Open-Cage Fullerene

      Dr. Chi-Shian Chen, Ting-Shen Kuo and Dr. Wen-Yann Yeh

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/chem.201601737

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      It's a trap! Organic compounds bearing a C=O or C≡N functional group are inserted into the new open-cage fullerene C63H4NO2(Ph)2(Py)(N2C6H4) containing a 20-membered ring orifice. The 1H NMR spectroscopy reveals substantial upfield shifts for the endohedral species owing to the strong shielding effect of the fullerene cage.

    2. Rotaxanes

      Efficient Synthesis of Cyclic Block Copolymer by Rotaxane Protocol by Linear/Cyclic Topology Transformation

      Stephanie Valentina, Dr. Takahiro Ogawa, Dr. Kazuko Nakazono, Dr. Daisuke Aoki and Prof. Dr. Toshikazu Takata

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/chem.201601266

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      Linear to cyclic: A gram-scale synthesis of cyclic block copolymer (CBC) was achieved by precise control on the movement of rotaxane components to change the polymer structure from linear to cyclic. This rotaxane protocol offers an alternative approach towards generating CBC in practical scales (see figure).

    3. Circularly Polarized Luminescence

      Bis(haloBODIPYs) with Labile Helicity: Valuable Simple Organic Molecules That Enable Circularly Polarized Luminescence

      César Ray, Dr. Esther M. Sánchez-Carnerero, Prof. Florencio Moreno, Prof. Beatriz L. Maroto, Prof. Antonia R. Agarrabeitia, Prof. María J. Ortiz, Prof. Íñigo López-Arbeloa, Prof. Jorge Bañuelos, Komlan D. Cohovi, Jamie L. Lunkley, Prof. Gilles Muller and Prof. Santiago de la Moya

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/chem.201601463

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      Inspiral CPL: Simple organic molecules (SOMs) based on bis(haloBODIPY) enable circularly polarized luminescence (CPL), bringing about a new structural design for technologically valuable CPL-SOMs. The design comprises together synthetic accessibility, helical lability, capacity for reversing the polarization handedness, and reactive functional groups, making possible photophysics modulation.

  34. Full Papers

    1. Polymers

      Polymer-Derived Silicoboron Carbonitride Foams for CO2 Capture: From Design to Application as Scaffolds for the in Situ Growth of Metal–Organic Frameworks

      Dr. Fabien Sandra, Dr. Martin Depardieu, Dr. Zineb Mouline, Prof. Gérard L. Vignoles, Prof. Yuji Iwamoto, Prof. Philippe Miele, Prof. Rénal Backov and Dr. Samuel Bernard

      Version of Record online: 12 MAY 2016 | DOI: 10.1002/chem.201600060

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      Catch if you can: Lightweight and porous silicoboron carbonitride foams have been synthesized by a template-assisted polymer-derived ceramic route. By following an in situ construction strategy, metal–organic frameworks (MOFs) have been grown directly within the open-cell structure of the foams to evaluate their potential for CO2 capture (see scheme).

    2. Anion Recognition

      Differential Recognition of Anions with Selectivity towards F by a Calix[6]arene–Thiourea Conjugate Investigated by Spectroscopy, Microscopy, and Computational Modeling by DFT

      Dr. Anita Nehra, Dr. Sateesh Bandaru, Deepthi S. Yarramala and Prof. Dr. Chebrolu Pulla Rao

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201600844

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      Bunch of flowers: The two calixarene-based triazole-appended thiourea conjugates 4L and 6L were investigated with regard to their anion-binding ability. Based on spectroscopic methods, DFT calculations, and SEM investigations a binding order for nineteen investigated anions was obtained. F was found to be best recognized by the composite 6L (see figure).

  35. Communications

    1. Directed Assembly

      Bis-Calix[4]arenes: From Ligand Design to the Directed Assembly of a Metal–Organic Trigonal Antiprism

      Marco Coletta, Dr. Ross McLellan, Paul Murphy, Bernhard T. Leube, Dr. Sergio Sanz, Rob Clowes, Dr. Kevin J. Gagnon, Dr. Simon J. Teat, Prof. Andrew I. Cooper, Prof. Martin J. Paterson, Prof. Euan K. Brechin and Dr. Scott J. Dalgarno

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201600762

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      Synthetic modification at the calix[4]arene (C[4]) methylene bridge offers a unique opportunity to influence cluster-forming chemistry. The synthesis of xylyl-tethered bis-C[4]s and their use as directing species in cluster-forming reactions is presented. These new ligands have been used to direct the assembly of a previously known FeIII2LnIII2 cluster, as well as a spectacular new metal–organic trigonal antiprism, the latter of which also displays thermal stability and uptake of N2 or H2 gas.

    2. Organic Chemistry

      Synthesis of Indolophanes by Photochemical Macrocyclization

      Magnus Pfaffenbach, Dipl.-Wirtschaftsing. Alexander Roller and Prof. Dr. Tanja Gaich

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201600835

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      C−H activation: The construction of highly strained 11–13-membered indolophane scaffolds was achieved by Witkop photocyclization (see scheme). Thereby, the prevailing regioselectivity of this reaction was completely reversed by the presence of a quaternary carbon center, exerting a strong Thorpe–Ingold effect on the system.The novel structure types feature atropisomerism and aromatic ring current effects, which both have been investigated.

    3. Drug Design

      Nucleosome Assembly Alters the Accessibility of the Antitumor Agent Duocarmycin B2 to Duplex DNA

      Tingting Zou, Seiichiro Kizaki, Dr. Ganesh N. Pandian and Prof. Hiroshi Sugiyama

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201600950

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      Nucleosome assembly influence: In vitro studies aimed at evaluating the alkylation level of duocarmycin B2 on nucleosomes with core and linker DNA were conducted using sequencing gel electrophoresis. Our results suggested that, in the nucleosome structure, the alkylating efficiencies of duocarmycin B2 were significantly decreased in core DNA and increased at the histone-free linker DNA sites compared with naked DNA conditions.

  36. Full Papers

    1. Catalysis | Hot Paper

      Regioselective Alkylative Carboxylation of Allenamides with Carbon Dioxide and Dialkylzinc Reagents Catalyzed by an N-Heterocyclic Carbene–Copper Complex

      Sandeep Suryabhan Gholap, Dr. Masanori Takimoto and Prof. Dr. Zhaomin Hou

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201601162

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      Alkylation and CO2 Incorporation: The alkylative carboxylation of allenamides with dialkylzinc reagents and carbon dioxide in the presence of a catalytic amount of an N-Heterocyclic Carbene (NHC)–copper complex was achieved. The reactions proceed through Cu-catalyzed carbozincation of allenamides with dialkylzinc reagents and the subsequent nucleophilic addition of the resulting alkenyl zinc species to CO2 (see scheme).

    2. Porphyrin Metalation | Hot Paper

      Zinc Porphyrin Metal-Center Exchange at the Solid–Liquid Interface

      Matthias Franke, Florencia Marchini, Prof. Dr. Norbert Jux, Prof. Dr. Hans-Peter Steinrück, Dr. Ole Lytken and Prof. Dr. Federico J. Williams

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201600634

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      Bureau de change: Zinc tetraphenylporphyrin (ZnTPP) adsorbed on Au(111) exchanges its Zn2+ centers with Cu2+ ions from a CuSO4 solution, forming CuTPP, in agreement with solution chemistry. However, contrary to solution chemistry, the surface ZnTPP does not demetalate under acid conditions.

    3. Electrocatalysis | Hot Paper

      Partially Hydrogenated Graphene Materials Exhibit High Electrocatalytic Activities Related to Unintentional Doping with Metallic Impurities

      Dr. Ondřej Jankovský, Alena Libánská, Daniel Bouša, Prof. David Sedmidubský, Dr. Stanislava Matějková and Prof. Zdeněk Sofer

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201600811

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      Unintentional doping: Partially hydrogenated graphene materials exhibit high electrocatalytic activities in the oxygen reduction reaction, as well as electrochemical sensing properties. However, such high performances are likely to originate not only from hydrogenation of the graphene, but also from metallic impurities introduced during synthesis.

    4. Lanthanides

      Fluoride Binding and Crystal-Field Analysis of Lanthanide Complexes of Tetrapicolyl-Appended Cyclen

      Dr. Octavia A. Blackburn, Dr. Alan M. Kenwright, Dr. Andrew R. Jupp, Prof. Jose M. Goicoechea, Prof. Paul D. Beer and Prof. Stephen Faulkner

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201601170

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      Magnetic anisotropy: This study shows the importance of the local crystal field in defining the behaviour of lanthanide complexes in solution. The observation that a well-defined N8 donor set can be used to change the sense of the magnetic anisotropy at a lanthanide centre has significant implications for control of spectroscopic properties in such systems (see scheme).

    5. Computational Chemistry

      Self-Assembly of Uranyl–Peroxide Nanocapsules in Basic Peroxidic Environments

      Dr. Pere Miró, Dr. Bess Vlaisavljevich, Dr. Adria Gil, Dr. Peter C. Burns, Dr. May Nyman and Dr. Carles Bo

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201600390

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      In charge: A wide range of uranyl–peroxide nanocapsules was synthesized by using very simple reactants in basic media. A DFT study of the speciation of the uranyl ions under different experimental conditions was carried out and explored the formation of dimeric species via a ligand exchange mechanism. The results shed light on the importance of the excess of peroxide and alkali counterions as a thermodynamic driving force towards the formation of larger uranyl–peroxide species (see figure).

    6. Molecular Devices

      Mechanism of Macroscopic Motion of Oleate Helical Assemblies: Cooperative Deprotonation of Carboxyl Groups Triggered by Photoisomerization of Azobenzene Derivatives

      Dr. Yoshiyuki Kageyama, Tomonori Ikegami, Yuta Kurokome and Prof. Dr. Sadamu Takeda

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201600426

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      Helices in motion: The mechanism of phototriggered macroscopic motions of hybrid assemblies of oleic acid and an azobenzene derivative was studied. Photoinduced deprotonation of carboxyl groups, which was investigated by potentiometric pH titration and FTIR spectroscopy, in cooperation with azobenzene photoisomerization (see figure) causes a morphological transition of the self-assembly, which in turn results in macroscopic dynamics.

    7. Carbone Structures

      Proton Affinities of Cationic Carbone Adducts [AC(PPh3)2]+ (A=Halogen, Hydrogen, Methyl) and Unusual Electronic Structures of the Cations and Dications [AC(H)(PPh3)2]2+

      Prof. Dr. Wolfgang Petz, Dr. Istemi Kuzu, Prof. Dr. Gernot Frenking, Dr. Diego M. Andrada, Prof. Dr. Bernhard Neumüller, Maximilian Fritz and Jörn E. Münzer

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201600525

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      Cationic carbone adducts: The structurally characterized cations [FC(PPh3)2]+ and [BrC(PPh3)2]+ and the protonated dication [FC(H)(PPh3)2]2+ possess unusual electronic structures and peculiar charge distributions (see scheme).

    8. Heterogeneous Catalysis

      Triazolyl-Based Molecular Gels as Ligands for Autocatalytic ‘Click’ Reactions

      Marco Araújo, Dr. Santiago Díaz-Oltra and Dr. Beatriu Escuder

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201600594

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      Supramolecular clickers: Supramolecular gels that are capable of coordinating copper(I) during their self-assembly process and building extended catalytic networks, have been developed. The wide distribution of metal throughout the fibers provides high catalytic activity for ‘click’ reactions and enables efficient self-replication of the heterogeneous catalyst (see scheme).

    9. Molecular Recognition

      Triazine-Carbon Nanotubes: New Platforms for the Design of Flavin Receptors

      Dr. María Isabel Lucío, Federica Pichler, Dr. José Ramón Ramírez, Prof. Antonio de la Hoz, Dr. Ana Sánchez-Migallón, Dr. Caroline Hadad, Dr. Mildred Quintana, Angela Giulani, Dr. Maria Victoria Bracamonte, Prof. Jose L. G. Fierro, Prof. Claudio Tavagnacco, Dr. María Antonia Herrero, Prof. Maurizio Prato and Dr. Ester Vázquez

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201600630

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      Receptors on rods: Artificial receptors of flavins are synthesised by the functionalisation of carbon nanotubes with 1,3,5-triazines (see figure). The ability of the nanotubes to recognise riboflavin is analysed by different techniques and the results highlight the major role of hydrogen bonds in the process. The possibility of modifying flavins and carbon nanotubes paves the way for the design of specific receptors in catalytic processes.

    10. B,N Heterocycles

      Regioselective Catalytic and Stepwise Routes to Bulky, Functional-Group-Appended, and Luminescent 1,2-Azaborinines

      Marius Schäfer, Julian Schäfer, Dr. Rian D. Dewhurst, Dr. William C. Ewing, Mirjam Krahfuß, Maximilian W. Kuntze-Fechner, Marius Wehner, Prof. Dr. Christoph Lambert and Prof. Dr. Holger Braunschweig

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201600653

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      The regioselective synthesis of 1,2-azaborinines is achieved using an unsymmetrical iminoborane through both catalytic and stepwise modular routes. The 1,2-azaborinine ring can be selectively functionalized in the 2- and/or 4-position through control of the stepwise reaction sequence, allowing access to vinyl-functionalized and redox-active, luminescent, donor-functionalized 1,2-azaborinines.

    11. Peptide Synthesis

      Solid-Phase Synthesis and Characterization of N-Terminally Elongated Aβ−3–x-Peptides

      Isaak Beyer, Dr. Nasrollah Rezaei-Ghaleh, Dr. Hans-Wolfgang Klafki, Dr. Olaf Jahn, Dr. Ute Haußmann, Prof. Dr. Jens Wiltfang, Prof. Dr. Markus Zweckstetter and Prof. Dr. Hans-Joachim Knölker

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201600892

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      N-Elongated Alzheimer′s peptides: Using a defined protocol for solid-phase peptide synthesis we have achieved an efficient synthesis of the three N-terminally elongated amyloid-β (Aβ) peptides Aβ−3–38, Aβ−3–40, and Aβ−3–42. Elongated Aβs are prone to aggregation into amyloid fibrils and are likely generated by β-site APP-cleaving enzyme 1 (BACE1)-independent processing of the amyloid precursor protein (APP).

    12. Reaction Mechanisms

      Eosin Y (EY) Photoredox-Catalyzed Sulfonylation of Alkenes: Scope and Mechanism

      Andreas Uwe Meyer, Karolína Straková, Dr. Tomáš Slanina and Prof. Dr. Burkhard König

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201601000

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      Metal-free conditions: Green light and eosin Y (EY) are sufficient in the presence of a terminal oxidant to cleanly convert a wide variety of sulfinate salts into vinyl sulfones. The detailed mechanistic study revealed that the reaction proceeds through the eosin radical cation (see scheme).

    13. Structure–Activity Relationships

      Host–Guest Binding-Site-Tunable Self-Assembly of Stimuli-Responsive Supramolecular Polymers

      Hao Yao, Miao Qi, Prof. Dr. Yuyang Liu and Prof. Dr. Wei Tian

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201601142

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      Two binding sites better than one? The β-cyclodextrin/azobenzene (β-CD/Azo) host–guest binding sites of the two synthesized polymers have a pronounced effect on the morphology and size of the resulting Y-shaped supramolecular polymer self-assemblies with thermo and photo dual-responsiveness (see figure).

    14. Organometallic Chemistry | Hot Paper

      Chiral Phosphate in Rhodium-Catalyzed Asymmetric [2+2+2] Cycloaddition: Ligand, Counterion, or Both?

      Dr. Marion Barbazanges, Dr. Elsa Caytan, Dr. Denis Lesage, Dr. Corinne Aubert, Prof. Louis Fensterbank, Prof. Vincent Gandon and Dr. Cyril Ollivier

      Version of Record online: 11 MAY 2016 | DOI: 10.1002/chem.201601188

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      Let's open the black box: The organometallic species involved in phosphate-directed Rh-catalyzed [2+2+2] cycloaddition of diynes to isocyanates are studied by using NMR spectroscopy, mass spectrometry, and DFT calculations, which provide physical evidence of the counterionic character of the chiral phosphate anion TRIP in an organometallic species.

    15. Metal Oxides

      Multishelled Metal Oxide Hollow Spheres: Easy Synthesis and Formation Mechanism

      Prof. Hongjing Wu, Prof. Guanglei Wu, Yanyan Ren, Prof. Xinghua Li and Prof. Liuding Wang

      Version of Record online: 10 MAY 2016 | DOI: 10.1002/chem.201504358

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      There go the spheres: Uniform multishelled NiO, Co3O4, ZnO, and Au@NiO hollow spheres were synthesized by a simple shell-by-shell self-assembly allowing for tuning of the size, thickness and shell numbers, opening up new opportunities for deeper understanding of the mechanisms of shell-by-shell self-assembly.

    16. Spin Crossover

      Guest-, Light- and Thermally-Modulated Spin Crossover in [FeII2] Supramolecular Helicates

      Mohanad Darawsheh, Dr. Leoni A. Barrios, Dr. Olivier Roubeau, Dr. Simon J. Teat and Dr. Guillem Aromí

      Version of Record online: 10 MAY 2016 | DOI: 10.1002/chem.201601080

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      Host–guest interactions shift spin crossover: A new bis(pyrazolylpyridine) ligand (H2L) has been used to prepare six functional X@[Fe2(H2L)3]3+ metallohelicates with entrapped guest ions (X=Cl, Br). Spin crossover between three magnetic states [LS–LS], [LS–HS], and [HS–HS] of the dinuclear FeII supramolecular helicates could be accessed by thermal or chemical changes, solvate -molecule or guest-ion exchange, and light irradiation.

    17. Surface Chemistry

      Decomposition of Fluorinated Graphene under Heat Treatment

      Dr. Jan Plšek, Dr. Karolina Anna Drogowska, Dr. Václav Valeš, Dr. Johan Ek Weis and Dr. Martin Kalbac

      Version of Record online: 10 MAY 2016 | DOI: 10.1002/chem.201600901

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      Intercalated H2O and OH species play an important role in the defluorination process of fluorinated graphene. Annealing at up to 700 K in ultrahigh vacuum caused gradual loss of fluorine and carbon by desorption of CO and HF species, as shown by temperature-programmed desorption (TPD). Defect formation in fluorinated graphene during heating was suggested. A small fraction of strongly bonded fluorine can however persist despite heating to 1000 K.

    18. C−H Activation

      Non-coordinating-Anion-Directed Reversal of Activation Site: Selective C−H Bond Activation of N-Aryl Rings

      Prof. Dr. Dawei Wang, Xiaoli Yu, Prof. Dr. Xiang Xu, Bingyang Ge, Xiaoli Wang and Yaxuan Zhang

      Version of Record online: 9 MAY 2016 | DOI: 10.1002/chem.201600293

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      Non-coordinating anion effect: Rh-catalyzed chemoselective C−H bond activation of anilides with alkenes has been realized by introducing a non-coordinating anion (OTf). This methodology provides an efficient means of selectively achieving N-aryl or C-aryl ring activation (see graphic).

    19. Ligand Design

      Boron-Metallated Borirenes and Bis(Borirenes)

      Prof. Dr. Holger Braunschweig, Dr. Mehmet Ali Celik, Dr. Rian D. Dewhurst, Dr. Katharina Ferkinghoff, Dr. Krzysztof Radacki and Felix Weißenberger

      Version of Record online: 9 MAY 2016 | DOI: 10.1002/chem.201600651

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      Running rings: Thermal reaction of the metalloborylene complex [{(η5-C5Me5)Fe(CO)2}(μ-B){Cr(CO)5}] in the presence of alkynes and diynes leads to the formation of a range of B-metallated borirenes and a bis(B-metallated borirene) with electron-donating and electron-withdrawing substituents through formal transfer of the metalloborylene moiety [(η5-C5Me5)(OC)2Fe(B:)] (see figure).

  37. Communications

    1. Organometallic Chemistry

      Fundamental Differences between Group 8 Metals: Unexpected Oxidation State Preferences and Mechanisms in Ruthenium Borylene Complex Formation

      Prof. Dr. Holger Braunschweig, Dr. Alexander Damme, Dr. Rian D. Dewhurst, Dr. Krzysztof Radacki, Felix Weißenberger, Dr. Benedikt Wennemann and Dr. Qing Ye

      Version of Record online: 9 MAY 2016 | DOI: 10.1002/chem.201601602

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      Nothing compares 2 Ru: The reaction of the salts K[Ru(CO)3(PMe3)(SiR3)] (R=Me, Et) with Br2BDur or Cl2BDur (Dur=2,3,5,6-Me4C6H) leads to both boryl and borylene complexes of divalent ruthenium. The latter distinctly contrasts from the analogous reactions with iron, which lead to low-valent borylene complexes, highlighting fundamental differences in oxidation-state preferences between iron and ruthenium.

    2. Metal Complexes

      Forging Unsupported Metal–Boryl Bonds with Icosahedral Carboranes

      Dr. Liban M. A. Saleh, Rafal M. Dziedzic, Dr. Saeed I. Khan and Prof. Dr. Alexander M. Spokoyny

      Version of Record online: 9 MAY 2016 | DOI: 10.1002/chem.201601292

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      A mercurial reagent: A mercurocarborane shows divergent reactivity with Pt or Pd precursors, delivering a Pt−B bond in one, and a rare Pd−Hg bond in the other (see scheme).

  38. Full Papers

    1. Library Synthesis

      One-Step Synthetic Access to Isosteric and Potent Anticancer Nitrogen Heterocycles with the Benzo[c]phenanthridine Scaffold

      Tamara N. Steinhauer, Dr. Ulrich Girreser, Dr. Christopher Meier, Prof. Dr. Mark Cushman and Prof. Dr. Bernd Clement

      Version of Record online: 6 MAY 2016 | DOI: 10.1002/chem.201600308

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      Isosteric nitrogen heterocycles: A large library of heterocycles, some possessing promising anticancer properties, with different substitution patterns is accessible by a facile one-step cyclization method through application of different aldehydes and distinct o-methylhetarenecarbonitrile components with diverse numbers of nitrogen atoms at various positions in the ring (see scheme).

    2. Organic Chemistry

      Fluorinated Musk Fragrances: The CF2 Group as a Conformational Bias Influencing the Odour of Civetone and (R)-Muscone

      Dr. Ricardo Callejo, Dr. Michael J. Corr, Mingyan Yang, Prof. Mingan Wang, Dr. David B. Cordes, Prof. Alexandra M. Z. Slawin and Prof. David O'Hagan

      Version of Record online: 6 MAY 2016 | DOI: 10.1002/chem.201600519

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      Molecular conformation control: The olfactory properties of two natural musk macrocycles can be selectively modified by placing CF2 groups in strategic locations. Compounds that retain the musky scent are showing reinforced conformations similar to the natural ketones. However, distorted conformations induced by CF2 groups are leading molecules without the characteristic musk odour (see figure).

  39. Concepts

    1. Supramolecular Chemistry

      You have free access to this content
      Advantages of Catalysis in Self-Assembled Molecular Capsules

      Lorenzo Catti, Qi Zhang and Prof. Dr. Konrad Tiefenbacher

      Version of Record online: 6 MAY 2016 | DOI: 10.1002/chem.201600726

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      Supramolecular hosts are increasingly investigated in catalysis due to three main conceptual advantages: 1) product selectivity, 2) substrate selectivity, and 3) the facilitation of multicatalyst tandem reactions (see figure). This Concept article discusses those advantages on the basis of prominent literature examples covering five different catalytically active host systems.

  40. Communications

    1. Asymmetric Synthesis | Hot Paper

      Dynamic Kinetic Resolution Approach for the Asymmetric Synthesis of Tetrahydrobenzodiazepines Using Transfer Hydrogenation by Chiral Phosphoric Acid

      Kosaku Horiguchi, Eri Yamamoto, Dr. Kodai Saito, Prof. Dr. Masahiro Yamanaka and Prof. Dr. Takahiko Akiyama

      Version of Record online: 6 MAY 2016 | DOI: 10.1002/chem.201601611

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      Organocatalysis: Asymmetric synthesis of tetrahydrobenzodiazepines was achieved by transfer hydrogenation of dihydrobenzodiazepines, involving dynamic kinetic resolution by means of a chiral phosphoric acid catalyst with benzothiazoline having a hydrogen-bonding donor substituent. This method was applicable to various racemic dihydrobenzodiazepines and the corresponding products were obtained in good yields with excellent diastereoselectivities and enantioselectivities (see scheme).

  41. Full Papers

    1. Imaging Agents | Hot Paper

      Iridium(III) Anthraquinone Complexes as Two-Photon Phosphorescence Probes for Mitochondria Imaging and Tracking under Hypoxia

      Lingli Sun, Yu Chen, Shi Kuang, Guanying Li, Ruilin Guan, Jiangping Liu, Prof. Liangnian Ji and Prof. Dr. Hui Chao

      Version of Record online: 4 MAY 2016 | DOI: 10.1002/chem.201600310

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      Hidden changes revealed: Four iridium(III) complexes were developed to act as two-photon phosphorescent mitochondrial-specific probes under hypoxia. The probes can image and track mitochondrial morphological changes in a hypoxic environment over a long period of time. Moreover, the probes can visualize hypoxic mitochondria in 3D multicellular spheroids (MCSs) and living zebrafish through two-photon phosphorescence imaging (see figure).

    2. Sila-Substitution

      Incorporation of β-Silicon-β3-Amino Acids in the Antimicrobial Peptide Alamethicin Provides a 20-Fold Increase in Membrane Permeabilization

      Dr. Julie L. H. Madsen, Dr. Claudia U. Hjørringgaard, Dr. Brian S. Vad, Prof. Dr. Daniel Otzen and Prof. Dr. Troels Skrydstrup

      Version of Record online: 4 MAY 2016 | DOI: 10.1002/chem.201600445

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      Permeabilized by silicon: Incorporation of β-silicon-β3-amino acids into the antimicrobial peptide alamethicin improves the membrane permeabilizing action of the peptide. A synthetic procedure to access β-silicon-β3-amino acids was developed and the amino acid analogues were incorporated into alamethicin at different positions (see scheme). The overall lipophilicity of the peptide was improved, resulting in a 20-fold increase in calcein release as compared with wild-type alamethicin.

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