Chemistry - A European Journal

Cover image for Vol. 15 Issue 6

January 26, 2009

Volume 15, Issue 6

Pages 1287–1531

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
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    1. Cover Picture: Solid-State Gas Sensors Developed from Functional Difluoroboradiazaindacene Dyes (Chem. Eur. J. 6/2009) (page 1287)

      Raymond Ziessel, Gilles Ulrich, Anthony Harriman, Mohammed A. H. Alamiry, Beverly Stewart and Pascal Retailleau

      Version of Record online: 20 JAN 2009 | DOI: 10.1002/chem.200990008

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      Highly porous polyacrylate beads coated with a dialkylaminostyryl boradiazaindacene dye are green, but emit light outside the range visible to the human eye. Exposure to trace amounts of acid (symbolized on the picture by a gas flow spiced with traces of HCl<100 ppb) turns the beads deep blue and switches on an intense red fluorescence. The process, which is fully reversed in the presence of base, also responds to alkylating reagents and phosgene. In their Full paper on page 1359 ff., R. Ziessel et al. report compelling evidence for this unique push–pull–pull mechanism

  2. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
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  3. Corrigendum

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
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    1. You have free access to this content
  4. News

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    9. Preview
  5. Concept

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
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    1. Heterocyclic Compounds

      Applications of Multicomponent Reactions to the Synthesis of Diverse Heterocyclic Scaffolds (pages 1300–1308)

      James D. Sunderhaus and Stephen F. Martin

      Version of Record online: 8 JAN 2009 | DOI: 10.1002/chem.200802140

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      So much from so little! The sequencing of multicomponent reactions (MCRs) with subsequent cyclization reactions is a powerful method for generating diverse collections of functionalized heterocyclic scaffolds (see scheme).

  6. Communications

    1. Top of page
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    4. Corrigendum
    5. News
    6. Concept
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    1. Copper Rotaxanes

      Electrochemically Driven Sequential Machines: An Implementation of Copper Rotaxanes (pages 1310–1313)

      Ganga Periyasamy, Jean-Paul Collin, Jean-Pierre Sauvage, Raphael D. Levine and Francoise Remacle

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200802249

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      It′s logical, captain! The operation of a set–reset logic machine based on the electrochemical switching of the redox states in a Cu rotaxane followed by ligand reorganization (Cu+(4) four-coordinate copper complex to Cu2+(5) five-coordinate copper complex; see scheme) is demonstrated.

    2. DNA Recognition

      A Fluorescent Bisanthracene Macrocycle Discriminates between Matched and Mismatch-Containing DNA (pages 1314–1318)

      Anton Granzhan and Marie-Paule Teulade-Fichou

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200802421

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      Mix and measure: A fluorescent bisanthracene macrocycle binds to fully matched and thymine-mismatched (TX) DNA duplexes by different binding modes, which may be differentiated spectroscopically. This behavior allows an easy fluorimetric or “naked-eye” discrimination between matched (X=A) and mismatch-containing (X=C, T, or G) oligonucleotides.

    3. Asymmetric Catalysis

      Asymmetric Gold-Catalyzed Hydroarylation/Cyclization Reactions (pages 1319–1323)

      Chung-Meng Chao, Maxime R. Vitale, Patrick Y. Toullec, Jean-Pierre Genêt and Véronique Michelet

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200802341

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      Gold efficiency: An efficient AuI catalytic system is described for the enantioselective hydroarylation/cyclization reaction of 1,6-enynes (see scheme). Use of the (R)-4-MeO-3,5-(tBu)2-MeOBIPHEP–gold complex led to clean rearrangements implying the formal addition of a carbon nucleophile (1,3,5-trimethoxybenzene, 1,3-dimethoxybenzene, pyrrole, 1,3,5-trimethoxy-2-bromobenzene and indole derivatives) to an alkene followed by a cyclization process.

    4. Cross-Coupling

      Negishi Cross-Couplings Compatible with Unprotected Amide Functions (pages 1324–1328)

      Georg Manolikakes, M.Sc. Zhibing Dong, Herbert Mayr, Jinshan Li and Paul Knochel

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200802349

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      Mild mannered: Unprotected amides and sulfonamides containing aryl bromides and iodides undergo, in the presence of S-PHOS, smooth Negishi cross-couplings with various zinc organometallic reagents, allowing the preparation of pharmaceutically relevant molecules (see scheme; S-PHOS=2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl).

    5. C[BOND]C Coupling

      Improved Palladium-Catalyzed Sonogashira Coupling Reactions of Aryl Chlorides (pages 1329–1336)

      Christian Torborg, Jun Huang, Thomas Schulz, Benjamin Schäffner, Alexander Zapf, Anke Spannenberg, Armin Börner and Matthias Beller

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200802444

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      Well matched: Novel palladium/heteroaryl-phosphines are introduced for Sonogashira reactions of aryl and heteroaryl chlorides including challenging substrates (see scheme). The desired coupling reactions proceed smoothly and tolerate various functional groups.

    6. Palladium Catalysis

      Phosphine-Free, Palladium-Catalyzed Arylation of Heterocycles through C[BOND]H Bond Activation with Pivalic Acid as a Cocatalyst (pages 1337–1340)

      Dongbing Zhao, Weida Wang, Shuang Lian, Fei Yang, Jingbo Lan and Jingsong You

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200802001

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      Ligand-free C-arylation: A general palladium-catalyzed C-arylation of N-heterocycles with aryl bromides has been performed without the presence of phosphines, the aid of CuI, or other metal additives by using pivalic acid as a cocatalyst (see scheme).

    7. Ionic Liquids

      Alkali Metal Oligoether Carboxylates—A New Class of Ionic Liquids (pages 1341–1345)

      Oliver Zech, Matthias Kellermeier, Stefan Thomaier, Eva Maurer, Regina Klein, Christian Schreiner and Werner Kunz

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200801806

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      On the way to greener ILs: The combination of a short oligoether carboxylate (CH3O-(CH2CH2O)3-CH2COO) with small alkali metal cations leads to the formation of a new class of ionic liquids that exhibit high thermal and electrochemical stability as well as low cytotoxicity.

  7. Full Papers

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    9. Preview
    1. Solid-Phase Synthesis

      Solid-Phase Synthesis of Peptide Libraries Combining α-Amino Acids with Inorganic and Organic Chromophores (pages 1346–1358)

      Katja Heinze and Klaus Hempel

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200801864

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      It works for metals too! Solid-phase peptide synthesis procedures were employed for the selective stepwise assembly of bis(terpyridine)ruthenium(II) chromophores and organic antennas to yield peptidic dyads. Electrochemistry, absorption spectroscopy and DFT calculations suggest electronically isolated chromophores in the ground state, while energy-transfer processes from the organic dye to the ruthenium complex occur in the excited dyads (see scheme).

    2. Gas Sensors

      Solid-State Gas Sensors Developed from Functional Difluoroboradiazaindacene Dyes (pages 1359–1369)

      Raymond Ziessel, Gilles Ulrich, Anthony Harriman, Mohammed A. H. Alamiry, Beverly Stewart and Pascal Retailleau

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200801911

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      All change please! Highly porous, spherical beads have been coated with near-IR absorbing difluoroboradiazaindacene dyes that possess tertiary amine fragments. When suspended in a gas flow spiced with trace amounts of acid or phosgene, the beads change color from green to blue and there is the concomitant appearance of bright red fluorescence. These processes are reversed on addition of ammonia or an organic amine.

    3. Enzyme catalysis

      Stereoselective Hydrogenation of Olefins Using Rhodium-Substituted Carbonic Anhydrase—A New Reductase (pages 1370–1376)

      Qing Jing, Krzysztof Okrasa and Romas J. Kazlauskas

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200801673

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      Protein as ligand: Replacing the active-site zinc in carbonic anhydrase (CA) by rhodium formed a new reductase for cofactor-free hydrogenation of olefins with hydrogen (see figure). Unlike free rhodium, this rhodium–protein hybrid, [Rh]-CA, was stereoselective (≈20:1) for cis-stilbene over trans-stilbene.

    4. Magnetic Properties

      Magnetic Interactions and Magnetic Anisotropy in Exchange Coupled 4f–3d Systems: A Case Study of a Heterodinuclear Ce3+–Fe3+ Cyanide-Bridged Complex (pages 1377–1388)

      Lorenzo Sorace, Claudio Sangregorio, Albert Figuerola, Cristiano Benelli and Dante Gatteschi

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200801638

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      Antisymmetry matters: A single-crystal magnetic and EPR study of a series of homologous Ln–M (Ln=LaIII, CeIII; M=FeIII, CoIII) complexes necessitated the introduction of isotropic, anisotropic and antisymmetric exchange terms to rationalise the observed behaviour (see figure). We propose this as a case study that may improve our understanding of the anisotropic magnetic properties of exchange coupled pairs containing orbitally non-degenerate ions.

    5. Nanomaterials

      Facile Functionalization of Multilayer Fullerenes (Carbon Nano-Onions) by Nitrene Chemistry and “Grafting from” Strategy (pages 1389–1396)

      Li Zhou, Chao Gao, Dandan Zhu, Weijian Xu, Fanqing Frank Chen, Amit Palkar, Luis Echegoyen and Eric Siu-Wai Kong

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200801642

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      Onions that don't make you cry: Multilayer fullerenes (carbon nano-onions, CNOs) are functionalized by direct [2+1] cycloaddition of nitrenes and subsequent use of the “grafting from” strategy of in situ ring-opening polymerization and atom transfer radical polymerization (see scheme). This comprehensive investigation of the chemistry of CNOs could lead to the fabrication of novel CNO-based nanomaterials and nanodevices.

    6. Photochemistry

      Ultrafast Internal Conversion in a Model Anthocyanin–Polyphenol Complex: Implications for the Biological Role of Anthocyanins in Vegetative Tissues of Plants (pages 1397–1402)

      Rita França Rodrigues, Palmira Ferreira da Silva, Karina Shimizu, Adilson A. Freitas, Sergey A. Kovalenko, Nikolaus P. Ernsting, Frank H. Quina and António Maçanita

      Version of Record online: 12 DEC 2008 | DOI: 10.1002/chem.200801207

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      Shedding light on anthocyanins: Light absorbed by a model anthocyanin–copigment complex dissipates into heat on a sub-picosecond timescale by internal conversion to the ground state (see graphic; MMF: 7-methoxy-4-methyl-flavylium, PCA: protocatechuic acid).

    7. Solar Cells

      Novel Zinc Porphyrin Sensitizers for Dye-Sensitized Solar Cells: Synthesis and Spectral, Electrochemical, and Photovoltaic Properties (pages 1403–1412)

      Cheng-Wei Lee, Hsueh-Pei Lu, Chi-Ming Lan, Yi-Lin Huang, You-Ren Liang, Wei-Nan Yen, Yen-Chun Liu, You-Shiang Lin, Eric Wei-Guang Diau and Chen-Yu Yeh

      Version of Record online: 18 DEC 2008 | DOI: 10.1002/chem.200801572

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      Colorful character: A diarylamino-substituted porphyrin (1) exhibits an overall efficiency of power conversion of 6.0 %. From a comparison of cell performance using the same TiO2 films, the green dye 1 (see figure) outperforms the best reported porphyrin sensitizer and gives a performance comparable to that of an N3-based dye-sensitized solar cell.

    8. Kinase Inhibitors

      MALDI-TOF Mass-Spectrometry-Based Versatile Method for the Characterization of Protein Kinases (pages 1413–1421)

      Noriyasu Kondo and Shin-Ichiro Nishimura

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200801650

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      A game of chemical tag: A MALDI-TOF mass-spectrometry-based quantitative characterization of human protein kinases is now possible by using novel synthetic peptides bearing both N-terminal stable isotope tags and C-terminal mass-spectrometry-sensitive enhancement reagents. This method allows rapid and precise kinetic analysis (see picture) of recombinant c-Abl kinases in vitro and direct monitoring of cellular kinase activity by using mouse B16 melanoma cells and human cancer K652 cells.

    9. Enzyme Catalysis

      Protein Flexibility and Metal Coordination Changes in DHAP-Dependent Aldolases (pages 1422–1428)

      Aurora Jiménez, Pere Clapés and Ramon Crehuet

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200801223

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      Reshaping active sites: Although crystallographic diffraction produces static structures, protein motion can be extracted by combining different experimental and computational techniques. The structure of two related aldolases shows that domain motions alter the coordination of the metal in the active site, which results in different catalytic power for the different conformations (see figure).

    10. Photochemistry

      transcis Photoisomerization of Azobenzene-Conjugated Dithiolato-Bipyridine Platinum(II) Complexes: Extension of Photoresponse to Longer Wavelengths and Photocontrollable Tristability (pages 1429–1439)

      Ryota Sakamoto, Shoko Kume, Manabu Sugimoto and Hiroshi Nishihara

      Version of Record online: 16 DEC 2008 | DOI: 10.1002/chem.200801593

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      Look into the light: Azobenzene-conjugated dithiolato-bipyridine platinum(II) complexes 13 show photoresponses at long wavelengths, high photoisomerization quantum yields, and thermal stability of the cis forms (see picture). In addition, complex 3 exhibits photocontrollable tristability in a single molecule, and can be interconverted by irradiation at 365, 405, and 578 nm.

    11. Magnetic Resonance Imaging

      Osmotically Shrunken LIPOCEST Agents: An Innovative Class of Magnetic Resonance Imaging Contrast Media Based on Chemical Exchange Saturation Transfer (pages 1440–1448)

      Enzo Terreno, Daniela Delli Castelli, Elisabetta Violante, Honorius M. H. F. Sanders, Nico A. J. M. Sommerdijk and Silvio Aime

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200801766

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      Honey, I Shrunk the Liposomes! Osmotically shrunken liposomes loaded with paramagnetic lanthanide(III) complexes (see figure) acting as shift reagents towards water protons represent an innovative class of highly sensitive agents for magnetic resonance imaging (MRI) applications. Their contrast is generated by a chemical exchange saturation transfer (CEST) mechanism.

    12. Ionic Liquids

      Speciation of Rare-Earth Metal Complexes in Ionic Liquids: A Multiple-Technique Approach (pages 1449–1461)

      Peter Nockemann, Ben Thijs, Kyra Lunstroot, Tatjana N. Parac-Vogt, Christiane Görller-Walrand, Koen Binnemans, Kristof Van Hecke, Luc Van Meervelt, Sergey Nikitenko, John Daniels, Christoph Hennig and Rik Van Deun

      Version of Record online: 2 JAN 2009 | DOI: 10.1002/chem.200801418

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      Rare-earth metal speciation in the ionic liquids betainium bis(trifluoromethylsulfonyl)imide and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (see figure) was investigated by a multiple-technique approach by using luminescence spectroscopy, 1H, 13C, and 89Y NMR spectroscopy and the synchrotron techniques EXAFS (extended X-ray absorption fine structure) and HEXS (high-energy X-ray scattering).

    13. Radicals

      Matrix Isolation and Spectroscopic Characterization of the Phenylperoxy Radical and Its Rearranged Products (pages 1462–1467)

      Artur Mardyukov and Wolfram Sander

      Version of Record online: 8 JAN 2009 | DOI: 10.1002/chem.200801546

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      Radical changes: The phenylperoxy radical 2 can be synthesized by the reaction of the phenyl radical 1 with 3O2. Irradiation of 2 with visible light produces the 2-oxepinoxy radical 3 in a clean reaction. Subsequent irradiation results in ring-opening and formation of several conformers of ketoketene 4. The radicals 2, 3, and 4 play an important role in the combustion of aromatic hydrocarbons.

    14. Heterocyclic Chemistry

      Regio- and Chemoselective Metalation of Chloropyrimidine Derivatives with TMPMgCl⋅LiCl and TMP2Zn⋅2 MgCl2⋅2 LiCl (pages 1468–1477)

      Marc Mosrin and Paul Knochel

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200801831

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      Fully functional! The pyrimidine ring is fully functionalized at the C5 and C2 positions under mild conditions by successive regio- and chemoselective zincation with TMP2Zn⋅2 MgCl2⋅2 LiCl (TMP=2,2,6,6-tetramethylpiperidyl) as the metalation agent (see scheme).

    15. Aluminophosphates

      Insights into Structure Direction of Microporous Aluminophosphates: Competition between Organic Molecules and Water (pages 1478–1490)

      Luis Gómez-Hortigüela, Joaquín Pérez-Pariente and Furio Corà

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200801458

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      Competitive molecules: A combination of experimental techniques and computational simulations of the AFI-type structure synthesised with different organic molecules has revealed the structure direction of microporous aluminophosphates (see picture). Water molecules play an important role during the crystallisation of these networks, by competing with organic structure-directing agents to be occluded within the AFI structure. TEA: triethylamine.

    16. Protein Design

      Organic Ligand Binding by a Hydrophobic Cavity in a Designed Tetrameric Coiled-Coil Protein (pages 1491–1498)

      Toshihisa Mizuno, Chinatsu Hasegawa, Yoichi Tanabe, Kenta Hamajima, Takashi Muto, Yoshinori Nishi, Masayuki Oda, Yuji Kobayashi and Toshiki Tanaka

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200800855

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      Plugging the hole: A de novo protein (AM2W in the schematic repersentation), which is a tetrameric coiled-coil protein with a designed hydrophobic cavity, exhibited affinity for size-complementary ligands. Ligand binding induced an increase in protein-structure stability, probably due to plugging of the cavity.

    17. Cross-Coupling

      Pincer Thioamide and Pincer Thioimide Palladium Complexes Catalyze Highly Efficient Negishi Coupling of Primary and Secondary Alkyl Zinc Reagents at Room Temperature (pages 1499–1507)

      Haibo Wang, Jing Liu, Yi Deng, Tianyin Min, Ganxiang Yu, Xiaojun Wu, Zhen Yang and Aiwen Lei

      Version of Record online: 19 DEC 2008 | DOI: 10.1002/chem.200801860

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      TONs of potential: Turnover numbers up to 6.1×106 were obtained in Negishi coupling of aryl iodides with primary and secondary alkyl zinc reagents promoted by pincer thioamide Pd complex 1 or pincer thioimide Pd complex 2 under mild conditions (see scheme). Alkyl zinc reagents with β-H atoms are also tolerated. The different reactivity of monoalkyl zinc and dialkyl zinc reagents was rationalized by a preliminary kinetic investigation.

    18. Crystal Engineering

      Hetero-Seeding and Solid Mixture to Obtain New Crystalline Forms (pages 1508–1515)

      Dario Braga, Fabrizia Grepioni, Lucia Maini, Marco Polito, Katia Rubini, Michele R. Chierotti and Roberto Gobetto

      Version of Record online: 29 DEC 2008 | DOI: 10.1002/chem.200800381

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      Tailoring crystal structures: Para-methyl benzyl alcohol (p-MeBA) and para-chloro benzyl alcohol (p-ClBA) are quasi-isostructural and share the same hydrogen bond patterns, but their crystals are not isomorphous. Formation of a new polymorph of p-MeBA was induced by hetero-seeding with powdered p-ClBA (see figure).

    19. Organometallics

      Reactions of Diazo Compounds with Alkenes Catalysed by [RuCl(cod)(Cp)]: Effect of the Substituents in the Formation of Cyclopropanation or Metathesis Products (pages 1516–1526)

      Marino Basato, Cristina Tubaro, Andrea Biffis, Marco Bonato, Gabriella Buscemi, Filippo Lighezzolo, Pamela Lunardi, Chiara Vianini, Franco Benetollo and Alessandro Del Zotto

      Version of Record online: 22 DEC 2008 | DOI: 10.1002/chem.200801211

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      Cyclopropanation versus metathesis: The reaction of diazo compounds with alkenes affords metathesis or cyclopropanation products depending on the steric and electronic properties of the substituents in the ruthenacyclobutane intermediate (see scheme; Cp=cyclopentadienyl).

  8. Preview

    1. Top of page
    2. Cover Picture
    3. Graphical Abstract
    4. Corrigendum
    5. News
    6. Concept
    7. Communications
    8. Full Papers
    9. Preview
    1. You have free access to this content
      Preview: Chem. Eur. J. 7/2009 (page 1531)

      Version of Record online: 20 JAN 2009 | DOI: 10.1002/chem.200990012

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