Chemistry - A European Journal

Cover image for Vol. 19 Issue 6

February 4, 2013

Volume 19, Issue 6

Pages 1837–2192

  1. Cover Pictures

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Minireview
    6. Communications
    7. Full Papers
    1. You have free access to this content
      Cover Picture: The Role of a Dipeptide Outer-Coordination Sphere on H2-Production Catalysts: Influence on Catalytic Rates and Electron Transfer (Chem. Eur. J. 6/2013) (page 1837)

      Dr. Matthew L. Reback, M. Sc. Bojana Ginovska-Pangovska, Dr. Ming-Hsun Ho, Dr. Avijita Jain, Dr. Thomas C. Squier, Dr. Simone Raugei, Dr. John A. S. Roberts and Dr. Wendy J. Shaw

      Version of Record online: 29 JAN 2013 | DOI: 10.1002/chem.201390013

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      Dipeptide-based ligands on Ni(P2N2)2 hydrogen production catalysts can alter both the rate and the overpotential of the resulting catalyst. The figure shows an overlay of the trajectories from molecular dynamics simulations and highlights the flexibility of the dipeptide ligands, which may aid in transient delivery of protons, but also limits the precise positioning achieved in enzymes. For more details see the Full Paper by S. Raugei, J. A. S. Roberts, W. J. Shaw and co-workers on page 1928 ff.

    2. You have free access to this content
      Back Cover: Selective Removal of Hydroxyl Groups from Graphene Oxide (Chem. Eur. J. 6/2013) (page 2196)

      Chun Kiang Chua and Prof. Martin Pumera

      Version of Record online: 29 JAN 2013 | DOI: 10.1002/chem.201390016

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      Selective removal of hydroxyl groups on graphene oxide has been achieved with ethanethiol–aluminium chloride complexes. The reduced graphene material exhibits improved electrochemical properties over its precursor graphite oxide (layered structure of graphite oxide depicted by the red layered wall of Antelope Canyon in Arizona). The selective defunctionalization of oxygen groups on graphene oxide opens up new opportunities for specific tailoring of graphene materials. For more information see the Full Paper by M. Pumera and C. K. Chua on page 2005 ff.

  2. Graphical Abstract

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Minireview
    6. Communications
    7. Full Papers
  3. News

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Minireview
    6. Communications
    7. Full Papers
  4. Minireview

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Minireview
    6. Communications
    7. Full Papers
    1. Enantioselective Synthesis

      Palladium- and Nickel-Catalyzed Alkenylation of Enolates (pages 1858–1871)

      Dr. Tobias Ankner, Dr. Casey C. Cosner and Prof. Dr. Paul Helquist

      Version of Record online: 16 JAN 2013 | DOI: 10.1002/chem.201202798

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      Close coupling: Coupling reactions of enolates with alkenyl halides are most commonly performed with various palladium catalysts and to a lesser extent with nickel catalysts (see scheme). Intra- and intermolecular, and enantioselective versions of these reactions have been developed and employed in a number of syntheses of natural products and other compounds of interest.

  5. Communications

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Minireview
    6. Communications
    7. Full Papers
    1. Microreactor Chemistry

      Synthesis of 1,2,3,4-Tetrahydroisoquinolines by Microreactor-Mediated Thermal Isomerization of Laterally Lithiated Arylaziridines (pages 1872–1876)

      Dr. Arianna Giovine, Dr. Biagia Musio, Dr. Leonardo Degennaro, Dr. Aurelia Falcicchio, Dr. Aiichiro Nagaki, Prof. Jun-ichi Yoshida and Prof. Renzo Luisi

      Version of Record online: 15 JAN 2013 | DOI: 10.1002/chem.201203533

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      Flow chemistry: A flow-microreactor-mediated synthesis of 1,2,3,4-tetrahydroisoquinolines (THIQs) is reported (see scheme). Starting from a laterally lithiated aziridine, a tetrahydroisoquinoline lithiated at C4 was generated by thermally induced isomerization. Because the reaction temperature is a crucial parameter, the exquisite thermal control possible in a flow-microreactor system allowed for fast, efficient, and highly reproducible synthesis of functionalized aziridines or THIQs.

    2. Semiconductors

      Mixed Organotin(IV) Chalcogenides: From Molecules to Sn-S-Se Semiconducting Thin Films Deposited by Spin-Coating (pages 1877–1881)

      Marek Bouška, Lukáš Střižík, Dr. Libor Dostál, Aleš Růžička, Prof. Dr. Antonín Lyčka, Ludvík Beneš, Milan Vlček, Jan Přikryl, Petr Knotek, Prof. Tomáš Wágner and Dr. Roman Jambor

      Version of Record online: 7 JAN 2013 | DOI: 10.1002/chem.201203573

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      Put the right spin on it: Mixed monomeric organotin(IV) chalcogenides of the general formula L2Sn2EX2 containing two terminal Sn–X (X=Se, Te) bonds were prepared and were tested as potential single-source precursors for the deposition of semiconducting thin films. Spin-coating deposition of [{2,6-(Me2NCH2)2C6H3}SnSe]2(μ-S), as the useful single-source precursor, provided amorphous Sn-S-Se semiconducting thin films.

    3. Crystallization

      Kinetically Controlled Crystallization for Synthesis of Monodispersed Coordination Polymer Nanocubes and Their Self-Assembly to Periodic Arrangements (pages 1882–1885)

      Dr. Ming Hu, Dr. Shinsuke Ishihara, Prof. Dr. Katsuhiko Ariga, Dr. Masataka Imura and Prof. Dr. Yusuke Yamauchi

      Version of Record online: 4 JAN 2013 | DOI: 10.1002/chem.201203138

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      Under control: A new concept for synthesizing monodispersed coordination polymer (CP) nanoparticles is established. By utilizing a chelating agent that is coordinated to the metal ions, the subsequent coordination process between metal ions and ligands is controllable (see figure). The obtained nanocubes with uniform sizes can be self-assembled into periodically ordered arrangements. This phenomenon is useful for sensing applications, such as those with responsive photonic crystals.

    4. Bridged Expanded Porphyrins

      Core-Modified meso-Aryl Hexaphyrins with an Internal Thiophene Bridge: Structure, Aromaticity, and Photodynamics (pages 1886–1890)

      Ganesan Karthik, Mahima Sneha, V. Prabhu Raja, Dr. Jong Min Lim, Prof. Dr. Dongho Kim, Dr. A. Srinivasan and Prof. Dr. Tavarekere K. Chandrashekar

      Version of Record online: 4 JAN 2013 | DOI: 10.1002/chem.201203737

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      Take the shortcut: The synthesis of core-modified meso aryl hexaphyrins with an internal thiophene bridge is reported. Introduction of the thiophene bridge alters the electronic structure as well as the π-electron circuit, resulting in increases in singlet lifetime (τs) and the two-photon absorption (TPA) cross-section. Furthermore, for the sulfur derivative, the internal bridging thiophene participates in a π-electron conjugation pathway.

    5. Metal–Organic Frameworks

      Crystalline Structural Intermediates of a Breathing Metal–Organic Framework That Functions as a Luminescent Sensor and Gas Reservoir (pages 1891–1895)

      Juan Xiao, Yuan Wu, Mian Li, Bao-Yu Liu, Prof. Dr. Xiao-Chun Huang and Prof. Dr. Dan Li

      Version of Record online: 4 JAN 2013 | DOI: 10.1002/chem.201203515

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      A rod-packing, breathing MOF (1), with two crystalline structural intermediates (1 a and 1 b; H2btca=benzotriazole-5-carboxylic acid) has been investigated. An underlying net approach for analyzing possible breathing MOFs, and a set of geometric parameters that can quantitatively describe such a breathing structural feature, are suggested. The 3D luminescent MOF is a promising candidate for specific sensors with exceptional sorption capacity.

    6. Bifunctional Inhibitors

      Targeting Matrix Metalloproteinases: Design of a Bifunctional Inhibitor for Presentation by Tumour-Associated Galectins (pages 1896–1902)

      Dr. Marco Bartoloni, Dr. Blanca E. Domínguez, Dr. Elisa Dragoni, Dr. Barbara Richichi, Dr. Marco Fragai, Dr. Sabine André, Prof. Hans-Joachim Gabius, Dr. Ana Ardá, Prof. Claudio Luchinat, Prof. Jesús Jiménez-Barbero and Prof. Cristina Nativi

      Version of Record online: 27 DEC 2012 | DOI: 10.1002/chem.201203794

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      A new strategy to exploit galectin presence to target matrix metalloproteinases (MMPs) is presented. A bifunctional conjugate with lactose and an inhibitor for MMPs is able to bind MMP and Gal-3 simultaneously. This compound might allow the lectin to attract the MMP inhibitor to the tumour site and to block protumoural activities of the lectin at the same time.

    7. Carbazoles

      Amino-Directed RhIII-Catalyzed C[BOND]H Activation Leading to One-Pot Synthesis of N[BOND]H Carbazoles (pages 1903–1907)

      Qibai Jiang, Dandan Duan-Mu, Dr. Wei Zhong, Prof. Dr. Hao Chen and Prof. Dr. Hong Yan

      Version of Record online: 7 JAN 2013 | DOI: 10.1002/chem.201203856

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      One-pot synthesis: An efficient amino-directed one-pot synthesis of N[BOND]H carbazoles from unprotected 2-aminobiaryl compounds is reported. The free amino unit acts as both a directing group for ortho C[BOND]H activation and a functional group for construction of an N-heterocyclic ring (see scheme).

    8. C[BOND]H Oxidation

      An Iron Catalyst for Oxidation of Alkyl C[BOND]H Bonds Showing Enhanced Selectivity for Methylenic Sites (pages 1908–1913)

      Irene Prat, Dr. Laura Gómez, Mercè Canta, Dr. Xavi Ribas and Dr. Miquel Costas

      Version of Record online: 19 DEC 2012 | DOI: 10.1002/chem.201203281

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      Many are called but few are chosen: A nonheme iron complex catalyzes the oxidation of alkyl C[BOND]H bonds by using H2O2 as the oxidant, showing an enhanced selectivity for secondary over tertiary C[BOND]H bonds (see scheme).

    9. Asymmetric Synthesis

      Enantioselective Construction of Spirooxindole Derivatives through [3+2] Annulation Catalyzed by a Bisthiourea as a Multiple-Hydrogen-Bond Donor (pages 1914–1918)

      Yan Shi, Aijun Lin, Haibin Mao, Zhijie Mao, Weipeng Li, Prof. Dr. Hongwen Hu, Prof. Dr. Chengjian Zhu and Prof. Dr. Yixiang Cheng

      Version of Record online: 23 DEC 2012 | DOI: 10.1002/chem.201202937

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      Anything between ureas? Spiro[isoxazolidine-3,3′-oxindole]s have been constructed by employing methyleneindolinones and nitrones as the starting materials through [3+2] annulation catalyzed by a bisthiourea. Products with three contiguous stereocenters, including one spiroquaternary stereocenter, are obtained in good yields with excellent enantio- and diastereoselectivity. The bisthiourea catalyst acts as a multiple-hydrogen-bond donor to simultaneously activate both substrates.

  6. Full Papers

    1. Top of page
    2. Cover Pictures
    3. Graphical Abstract
    4. News
    5. Minireview
    6. Communications
    7. Full Papers
    1. G-Quadruplexes

      Carbohydrate–DNA Interactions at G-Quadruplexes: Folding and Stability Changes by Attaching Sugars at the 5′-End (pages 1920–1927)

      Dr. Irene Gómez-Pinto, Empar Vengut-Climent, Dr. Ricardo Lucas, Dr. Anna Aviñó, Prof. Dr. Ramón Eritja, Prof. Dr. Carlos González and Dr. Juan Carlos Morales

      Version of Record online: 11 JAN 2013 | DOI: 10.1002/chem.201203902

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      Sweetening G-quadruplexes: Carbohydrate–DNA contacts are observed in a G-quadruplex context. Mono- and disaccharides attached to the 5′ end of the thrombin-binding aptamer (TBA) are capable of stabilizing the conjugate with respect to the spacer-TBA control. A detailed structure elucidation of the fucose–TBA conjugate shows sugar stacking on the guanine tetrad together with methyl–methyl van der Waals interactions and a possible hydrogen bond (see figure).

    2. Homogeneous Catalysis

      The Role of a Dipeptide Outer-Coordination Sphere on H2-Production Catalysts: Influence on Catalytic Rates and Electron Transfer (pages 1928–1941)

      Dr. Matthew L. Reback, M. Sc. Bojana Ginovska-Pangovska, Dr. Ming-Hsun Ho, Dr. Avijita Jain, Dr. Thomas C. Squier, Dr. Simone Raugei, Dr. John A. S. Roberts and Dr. Wendy J. Shaw

      Version of Record online: 11 DEC 2012 | DOI: 10.1002/chem.201202849

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      Peptide-like scaffold enhancements: [Ni(PPh2NPh-dipeptide2)2]2+ electrocatalysts containing dipeptides in the outer-coordination sphere (such as depicted) show an impact on rate and overpotential. Amide functional groups enhance the rate modestly, while polar and aromatic groups do not impact catalysis. This work shows the impact that an outer-coordination sphere can have on a molecular catalyst system.

    3. Oxidation

      Theoretical Study of the Oxidation of Phenolates by the [Cu2O2(N,N′-di-tert-butylethylenediamine)2]2+ Complex (pages 1942–1954)

      Dr. Yan Fang Liu, Prof. Jian Guo Yu, Prof. Per E. M. Siegbahn and Prof. Margareta R. A. Blomberg

      Version of Record online: 4 JAN 2013 | DOI: 10.1002/chem.201203052

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      Putting it to DBED: The mechanism of phenolate oxidation into quinone by the [Cu2O2(DBED)2]2+ complex was studied by using the hybrid density functional B3LYP*. After cleavage of the O[BOND]O bond, phenolate coordinates to the bis-μ-oxodicopper(III) complex, thus giving experimentally characterized intermediate A. The oxidation of the phenolate into a quinone through experimentally observed intermediates B and C is also described (see scheme).

    4. Self-Assembly

      Water-Soluble and pH-Responsive Polymeric Nanotubes from Cyclic Peptide Templates (pages 1955–1961)

      Robert Chapman, Prof. Gregory G. Warr, Prof. Sébastien Perrier and Prof. Dr. Katrina A. Jolliffe

      Version of Record online: 7 JAN 2013 | DOI: 10.1002/chem.201203602

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      Nanotubes wear polymer coats: Water-soluble, polymer-coated nanotubes were formed by self-assembly of cyclic peptides–polymer conjugates. Assembly of poly(acrylic acid)-coated conjugates can be controlled by changing the pH (see scheme).

    5. Antitumor Agents

      Fully Synthetic Self-Adjuvanting Thioether-Conjugated Glycopeptide[BOND]Lipopeptide Antitumor Vaccines for the Induction of Complement-Dependent Cytotoxicity against Tumor Cells (pages 1962–1970)

      Dr. Hui Cai, Zhan-Yi Sun, Zhi-Hua Huang, Lei Shi, Prof. Dr. Yu-Fen Zhao, Prof. Dr. Horst Kunz and Prof. Dr. Yan-Mei Li

      Version of Record online: 23 DEC 2012 | DOI: 10.1002/chem.201203709

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      You do it to yourself: Self-adjuvanting vaccines with a tumor-associated MUC1 glycopeptide and the TLR2 ligand lipopeptide Pam3CSK4 were synthesized. Three-component vaccines induced strong antitumor immune responses that induced tumor-cell death (see scheme).

    6. Imaging Agents

      Ruthenium Complexes with Hydrophobic Ligands That Are Key Factors for the Optical Imaging of Physiological Hypoxia (pages 1971–1977)

      Dr. Hirokazu Komatsu, Kazuki Yoshihara, Dr. Hisatsugu Yamada, Dr. Yu Kimura, Dr. Aoi Son, Prof. Dr. Sei-ichi Nishimoto and Dr. Kazuhito Tanabe

      Version of Record online: 20 DEC 2012 | DOI: 10.1002/chem.201202809

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      Optimal imaging: The phosphorescence emission of ruthenium complexes was applied to the optical imaging of physiological hypoxia. Three complexes with hydrophobic substituents on the phenanthroline ligand were characterized; their emission was quenched by molecular oxygen. Among the complexes synthesized in this study, a pyrene chromophore-linked ruthenium complex, Ru-Py, exhibited the optimal properties for the imaging of hypoxia (see figure).

    7. Cyclization

      1-(2′-Anilinyl)prop-2-yn-1-ol Rearrangement for Oxindole Synthesis (pages 1978–1985)

      Dr. Prasath Kothandaraman, Bing Qin Koh, Dr. Taweetham Limpanuparb, Prof. Dr. Hajime Hirao and Prof. Dr. Philip Wai Hong Chan

      Version of Record online: 30 NOV 2012 | DOI: 10.1002/chem.201202606

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      Alcohols to oxindoles: A chemoselective synthetic method that relies on NIS-mediated cycloisomerization reactions of 1-(2′-anilinyl)prop-2-yn-1-ols to gem-3-(diiodomethyl)indolin-2-ones and 2-(iodomethylene)indolin-3-ones was developed (see scheme; NIS=N-iodosuccinimide). Secondary and tertiary alcoholic substrates exclusively gave the 3- and 2-oxindole products, respectively; in the case of the latter, the transformation features an unprecedented double 1,2-OH and 1,2-alkyl migration relay.

    8. Coordination Polymers

      Salen-Based Coordination Polymers of Manganese and the Rare-Earth Elements: Synthesis and Catalytic Aerobic Epoxidation of Olefins (pages 1986–1995)

      Dr. Asamanjoy Bhunia, Meike A. Gotthardt, Munendra Yadav, Dr. Michael T. Gamer, Dr. Andreas Eichhöfer, Dr. Wolfgang Kleist and Prof. Dr. Peter W. Roesky

      Version of Record online: 28 DEC 2012 | DOI: 10.1002/chem.201203636

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      Coordination polymer catalysts: A number of manganese- and lanthanide-containing 1D coordination polymers have been synthesized, in which the manganese atoms are in a salen-type scaffold (see figure; salen=N,N′-bis(4-carboxysalicylidene)ethylenediamine). The manganese–gadolinium compound was used as a catalyst in the liquid-phase epoxidation of trans-stilbene with molecular oxygen, which resulted in the formation of stilbene oxide.

    9. Chromophores

      Computational Design, Synthesis, and Mechanochromic Properties of New Thiophene-Based π-Conjugated Chromophores (pages 1996–2004)

      Dr. Giacomo Prampolini, Prof. Fabio Bellina, Dr. Malgorzata Biczysko, Dr. Chiara Cappelli, Luciano Carta, Dr. Marco Lessi, Dr. Andrea Pucci , Prof. Giacomo Ruggeri and Prof. Vincenzo Barone

      Version of Record online: 23 DEC 2012 | DOI: 10.1002/chem.201203672

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      Get smart! A new family of luminescent chromophores has been designed. The procedure used allowed the selection of the best candidate for the preparation of a novel mechanoresponsive “smart” device. The integration of the computational and experimental techniques defines an efficient protocol that can be applied when a selection among very similar dye candidates is required (see figure).

    10. Graphene

      Selective Removal of Hydroxyl Groups from Graphene Oxide (pages 2005–2011)

      Chun Kiang Chua and Prof. Martin Pumera

      Version of Record online: 18 JAN 2013 | DOI: 10.1002/chem.201204002

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      Selective defunctionalisation! The use of the ethanethiol–aluminium chloride complex has allowed the selective defunctionalisation of hydroxyl moieties on graphene oxide surfaces (see figure). The resulting graphene materials exhibited enhanced heterogeneous electron-transfer rates, a lower charge-transfer resistance and improved conductivity as compared to the parent graphene oxide.

    11. Topochemistry

      Structural Observations of Heterometallic Uranyl Copper(II) Carboxylates and Their Solid-State Topotactic Transformation upon Dehydration (pages 2012–2022)

      Jakub Olchowka, Clément Falaise, Dr. Christophe Volkringer, Dr. Natacha Henry and Dr. Thierry Loiseau

      Version of Record online: 23 DEC 2012 | DOI: 10.1002/chem.201203748

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      As strong as an oxo bridge: A series of UO22+[BOND]Cu2+ polycarboxylates with characteristic heterometallic bridging oxo groups (U[DOUBLE BOND]O[BOND]Cu) were synthesized; dehydration induced atomic rearrangement with the stabilization of a crystalline anhydrous form (see scheme).

    12. Exchange Interactions

      Sulfinylnitriles: Sulfinyl–Metal Exchange–Alkylation Strategies (pages 2023–2029)

      Dinesh Nath and Prof. Fraser F. Fleming

      Version of Record online: 23 DEC 2012 | DOI: 10.1002/chem.201203174

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      Sulfinyl–metal exchange: Organometallic addition to sulfinylnitriles triggers a facile exchange route to C- or N-metalated nitriles (see scheme). Alkylations afford quaternary, tertiary, and alkenenitriles even in the presence of carbonyl functionality and highly acidic protons.

    13. Homogeneous Catalysis

      Mechanistic Studies on the Roles of the Oxidant and Hydrogen Bonding in Determining the Selectivity in Alkene Oxidation in the Presence of Molybdenum Catalysts (pages 2030–2040)

      Prakash Chandra, Swati L. Pandhare, Dr. Shubhangi B. Umbarkar, Dr. Mohan K. Dongare and Dr. Kumar Vanka

      Version of Record online: 4 JAN 2013 | DOI: 10.1002/chem.201202597

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      Molybdenum-catalysed oxidation: Calculations performed by using density functional theory indicate that different mechanisms compete during the homogeneous catalysis of olefin oxidation carried out in the presence of molybdenum-based catalysts (see scheme).

    14. Carbon Nitrides

      Formation and Characterization of Melam, Melam Hydrate, and a Melam–Melem Adduct (pages 2041–2049)

      Eva Wirnhier, Maria B. Mesch, Prof. Dr. Jürgen Senker and Prof. Dr. Wolfgang Schnick

      Version of Record online: 19 DEC 2012 | DOI: 10.1002/chem.201203340

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      You're twisting my melam, man: Solvothermal reactions opened the door to the synthesis not only of bulk melam, [C3N3(NH2)2]2NH, but also of further crystalline intermediates in the carbon nitride condensation process. Whereas the formation of melam and a melam–melem adduct benefited from slower reaction kinetics, single crystals of melam hydrate are formed under hydrothermal conditions (see scheme).

    15. Halogen Bonding

      Halogen Bonding between Anions and Iodoperfluoroorganics: Solution-Phase Thermodynamics and Multidentate-Receptor Design (pages 2050–2058)

      Mohammed G. Sarwar, Bojan Dragisić, Elena Dimitrijević and Prof. Mark S. Taylor

      Version of Record online: 28 DEC 2012 | DOI: 10.1002/chem.201202689

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      The I's that bind: Halogen-bonding interactions between halide anions and iodoperfluoroalkanes and iodoperfluoroarenes in moderately polar organic solvents, such as acetone and acetonitrile, are of appreciable strength (see figure). Several multidentate-receptor architectures were also evaluated. Structure–activity relationships, computational studies, thermodynamics from van 't Hoff plot analysis, and solvent effects are presented.

    16. Nanocatalysis

      Cooperative Effects in Catalytic Hydrogenation Regulated by both the Cation and Anion of an Ionic Liquid (pages 2059–2066)

      Wenwen Zhu, Yinyin Yu, Prof. Dr. Hanmin Yang, Li Hua, Yunxiang Qiao, Xiuge Zhao and Prof. Dr. Zhenshan Hou

      Version of Record online: 19 DEC 2012 | DOI: 10.1002/chem.201202707

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      Going hot and cold: Functionalized ionic liquids have been synthesized and used as stabilizers, modifying agents, and thermoregulated supports for both Pd and Rh nanoparticles. The ionic-liquid-stabilized nanoparticles show excellent catalytic activity and selectivity in the hydrogenation of α,β-unsaturated aldehydes/ketones and aromatic nitro compounds. Clean separation of the nanocatalysts from the solvent and product has been achieved simply by adjusting the temperature of the mixture (see graphic).

    17. Donor–Acceptor Systems

      Efficient Synthesis of a Regioregular Oligothiophene Photovoltaic Dye Molecule, MK-2, and Related Compounds: A Cooperative Hypervalent Iodine and Metal-Catalyzed Synthetic Route (pages 2067–2075)

      Dr. Toshifumi Dohi, Nobutaka Yamaoka, Shota Nakamura, Kohei Sumida, Koji Morimoto and Prof. Dr. Yasuyuki Kita

      Version of Record online: 23 DEC 2012 | DOI: 10.1002/chem.201203503

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      Organic dyes: An efficient route has been established to the core structure of donor–acceptor head-to-tail-linked regioregular oligothiophenes. The versatility of this new approach is highlighted in the dramatic improvement of the yield (ca. 59 % overall yield) of MK-2, a high-performance organic dye for photovoltaic applications (see scheme; Hex=hexyl).

    18. Peptides

      Harnessing the Flexibility of Peptidic Scaffolds to Control their Copper(II)-Coordination Properties: A Potentiometric and Spectroscopic Study (pages 2076–2088)

      Ana Fragoso, Dr. Pedro Lamosa, Prof. Rita Delgado and Dr. Olga Iranzo

      Version of Record online: 4 JAN 2013 | DOI: 10.1002/chem.201203545

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      Fasten the belt: A cyclic decapeptide, C-Asp, and its linear counterpart, O-Asp, have been designed to coordinate Cu2+ ions as metalloenzymes do, mainly through the side-chain functionalities. Although both peptidic scaffolds contain the same metal-ion-coordinating amino acids, that is, three His and one Asp residues, and are well-tuned for binding, cyclization generates a more stable and rigid CuHL species that presents a slower metal-ion exchange rate.

    19. Host–Guest Chemistry

      Molecular Daisy Chains: Synthesis and Aggregation Studies of an Amphiphilic Molecular Rod (pages 2089–2101)

      Dr. Jürgen Rotzler, Sylvie Drayss, Dr. Oliver Hampe, Dr. Daniel Häussinger and Prof. Dr. Marcel Mayor

      Version of Record online: 7 JAN 2013 | DOI: 10.1002/chem.201202498

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      Oligomeric daisy chains: A water-soluble cyclophane as the loop subunit, monofunctionalized with a molecular rod, has been synthesized to introduce a new binding motif for mechanically interlinked oligomers (see figure). This hermaphroditic compound forms [c2]daisy chains in polar solvents over a wide range of concentrations. Furthermore, evidence for the formation of larger, mechanically interlinked oligomers above the critical aggregation concentration has been obtained.

    20. Stereocontrolled Synthesis

      A New Access Route to Functionalized Cispentacins from Norbornene β-Amino Acids (pages 2102–2107)

      Dr. Loránd Kiss, Maria Cherepanova, Dr. Enikő Forró and Prof. Ferenc Fülöp

      Version of Record online: 19 DEC 2012 | DOI: 10.1002/chem.201203183

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      Ringing the changes: An efficient and simple new stereocontrolled access route to novel disubstituted cispentacin derivatives with multiple stereogenic centers from norbornene β-lactam has been developed (see scheme). The synthesis involves olefinic-bond functionalization by dihydroxylation followed by oxidative ring cleavage and transformation of the dialdehyde intermediate through a Wittig reaction.

    21. Macrocycles

      Exploiting Aggregation To Achieve Phase Separation in Macrocyclization (pages 2108–2113)

      Anne-Catherine Bédard and Prof. Dr. Shawn K. Collins

      Version of Record online: 28 DEC 2012 | DOI: 10.1002/chem.201203433

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      PEGing out macrocycles: Macrocyclization through Glaser–Hay coupling can be conducted at high concentrations by exploiting solvent mixtures containing poly(ethylene glycol)400 (PEG400)/MeOH (see scheme). Surface tension measurements, UV spectroscopy, and chemical tagging demonstrate the dependence of the yield and selectivity on the aggregation of PEG400 and its ability to preferentially solubilize organic substrates, resulting in a phase separation from the catalyst system.

    22. Anion Binding

      Counterion Dynamics in an Interpenetrated Coordination Cage Capable of Dissolving AgCl (pages 2114–2121)

      Sabrina Freye, David M. Engelhard, Dr. Michael John and Prof. Dr. Guido H. Clever

      Version of Record online: 19 DEC 2012 | DOI: 10.1002/chem.201203086

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      Cleverly unlocked: The solvent- and temperature-dependent dynamic behavior of anions occupying the central and the two outer pockets of a self-assembled, interpenetrated double cage is presented. Addition of two equivalents of solid AgCl led to exchange of the BF4 ions in the outer pockets by chloride (see figure). NOE data shows that the allosteric binding is accompanied by compression along and torsion around the Pd4 axis.

    23. Zeolites

      Multiple Zeolite Structures from One Ionic Liquid Template (pages 2122–2130)

      José María Martínez Blanes, Dr. Bartłomiej M. Szyja, Dr. Francisca Romero-Sarria, Dr. Miguel Ángel Centeno, Prof. Emiel J. M. Hensen, Prof. José Antonio Odriozola and Dr. Svetlana Ivanova

      Version of Record online: 19 DEC 2012 | DOI: 10.1002/chem.201202556

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      Driven to develop: Three different zeolite families were synthesized by using a short-chain alkylimidazolium ionic liquid as the template (see figure). The importance of the silicon source, chemical environment, and the template-gel components in driving the formation of the different zeolite structures are demonstrated by a molecular simulation study and experimental techniques.

    24. Amination

      An Examination of the Palladium/Mor-DalPhos Catalyst System in the Context of Selective Ammonia Monoarylation at Room Temperature (pages 2131–2141)

      Pamela G. Alsabeh, Dr. Rylan J. Lundgren, Dr. Robert McDonald, Dr. Carin C. C. Johansson Seechurn, Dr. Thomas J. Colacot and Prof. Dr. Mark Stradiotto

      Version of Record online: 4 JAN 2013 | DOI: 10.1002/chem.201203640

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      More and Mor-DalPhos: Investigations into the Pd/Mor-DalPhos catalyst system enabled the development of an effective precatalyst for the Buchwald–Hartwig amination of (hetero)aryl (pseudo)halides employing ammonia at room temperature (see scheme; Mor-DalPhos=di(1-adamantyl)-2-morpholinophenylphosphine).

    25. Mesoporous Materials

      When Mesoporous Silica Meets the Alkaline Polyelectrolyte: A Controllable Synthesis of Functional and Hollow Nanostructures with a Porous Shell (pages 2142–2149)

      Liang You, Tianyi Wang and Prof. Jianping Ge

      Version of Record online: 3 DEC 2012 | DOI: 10.1002/chem.201203308

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      Meeting of minds: An improved surface-protected etching method by using mesoporous silica as the template and an alkaline polyelectrolyte as both the protecting and etching agent was developed to prepare a SiO2 nanotube with a porous shell (see scheme). The polyelectrolytes attached to the template not only create a localized alkaline environment, but also effectively protect the silica surface, whereas the mesopore channels accelerate the diffusion of etchant throughout the template. These actions facilitate the formation of hollow structures in a fully controllable manner.

    26. Cascade Reactions

      Pd-Catalyzed Ring Assembly by Vinylation and Intramolecular Heck Coupling: A Versatile Strategy Towards Functionalized Azadibenzocyclooctynes (pages 2150–2157)

      Dr. Michael Jäger , Dr. Helmar Görls, Dr. Wolfgang Günther and Prof. Dr. Ulrich S. Schubert 

      Version of Record online: 19 DEC 2012 | DOI: 10.1002/chem.201202790

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      Cascade ring assembly: A modular route for construction of the azocine scaffold was developed that allows efficient large-scale preparation in 1–2 steps. The novel N-benzoyl octyne was prepared and isolated by simple crystallization, and displays high reactivity in a typical copper-free click reaction (see scheme).

    27. Coordination Chemistry

      Three-Coordinate Nickel(I) Complexes Stabilised by Six-, Seven- and Eight-Membered Ring N-Heterocyclic Carbenes: Synthesis, EPR/DFT Studies and Catalytic Activity (pages 2158–2167)

      Dr. Michael J. Page, Wei Y. Lu, Rebecca C. Poulten, Dr. Emma Carter, Dr. Andrés G. Algarra, Dr. Benson M. Kariuki, Prof. Stuart A. Macgregor, Dr. Mary F. Mahon, Prof. Kingsley J. Cavell, Dr. Damien M. Murphy and Prof. Michael K. Whittlesey

      Version of Record online: 4 JAN 2013 | DOI: 10.1002/chem.201202950

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      Three of a kind: A series of three-coordinate NiI complexes stabilised by N-aryl substituted six-, seven- and eight-membered ring N-heterocyclic carbenes (see figure) have been prepared and characterised by a combination of X-ray crystallography, EPR spectroscopy and DFT calculations. The complexes are precursors for the Kumada cross-coupling of aryl chlorides and fluorides.

    28. Oligosaccharide Mimics

      N[BOND]O Bond as a Glycosidic-Bond Surrogate: Synthetic Studies Toward Polyhydroxylated N-Alkoxypiperidines (pages 2168–2179)

      Dr. Gaëlle Malik, Angélique Ferry, Dr. Xavier Guinchard, Dr. Thierry Cresteil and Prof. Dr. David Crich

      Version of Record online: 19 DEC 2012 | DOI: 10.1002/chem.201202374

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      NO glycosidic bonds: The synthesis of highly functionalized dialdehydes from sodium cyclopentadienylide is described. The dialdehydes undergo double reductive aminations with N-alkoxyamines for the synthesis of various N-alkoxypiperidines, which, after deprotection, furnish glycomimetics with an “anomeric” hydroxylamine as an achiral surrogate for the glycosidic bond (see scheme; Bn: benzyl; NAP: naphthylmethyl). The energy for the nitrogen inversion in these series is approximately 15 kcal mol−1, which theoretically enables molecular adaptability to biological targets.

    29. Cascade Reactions

      Carbophilic 3-Component Cascades: Access to Complex Bioactive Cyclopropyl Diindolylmethanes (pages 2180–2184)

      Nigel M. Groome, Elghareeb E. Elboray, Dr. Martyn W. Inman, Prof. H. Ali Dondas, Dr. Roger M. Phillips, Colin Kilner and Prof. Ronald Grigg

      Version of Record online: 20 DEC 2012 | DOI: 10.1002/chem.201202647

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      Cascades against cancer: Pd0-catalysed construction of 1,6-enynes occurs in good yield. Combination with a threefold excess of an indole and platinum(II) chloride (5 mol %) furnishes the cyclopropyl diindolylmethanes (see scheme). This is a two-step process with PtII generating azabicyclo[4.1.0]hept-4-enes and a proton-catalysed Mannich–Michael reaction that is responsible for the double indole addition/ring opening to furnish the cyclopropyl diindolylmethanes.

    30. Kinetics

      Catalytic Mechanism of the Arylsulfatase Promiscuous Enzyme from Pseudomonas Aeruginosa (pages 2185–2192)

      Dr. Tiziana Marino, Prof. Nino Russo and Prof. Marirosa Toscano

      Version of Record online: 28 DEC 2012 | DOI: 10.1002/chem.201201943

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      A quantum-mechanical method based on DFT was used to investigate the catalytic mechanism of the hydrolysis of the two substrates p-nitrophenyl- sulfate (PNPS) and p-nitrophenyl-phosphate (PNPP) by the promiscuous enzyme (see scheme). Calculations were carried out with the aim of highlighting eventual mechanistic differences in the catalysis of these two substrates that can validate the comparable kinetics experimentally observed.

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