Chemistry - A European Journal

Cover image for Chemistry - A European Journal

December 7, 2007

Volume 13, Issue 35

Pages 9723–10003

  1. Cover Picture

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    1. Cover Picture: Chemical Clockwise Tridifferentiation of α- and β-Cyclodextrins: Bascule-Bridge or Deoxy-Sugars Strategies (Chem. Eur. J. 35/2007) (page 9723)

      Olivia Bistri, Pierre Sinaÿ, Jesùs Jiménez Barbero and Matthieu Sollogoub

      Version of Record online: 27 NOV 2007 | DOI: 10.1002/chem.200790135

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      A bascule-bridge strategy…has been delineated for the highly selective clockwise deprotection of a reversibly capped cyclodextrin. This concept is illustrated on the cover, created by Adrien and Karine Leroy, displaying the

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      Moct (Palace Bridge), a famous bascule bridge in Saint Petersburg, operating only a short distance away from the historical University where Mendeleev proposed his periodic table. This is one of two tools, proposed by M. Sollogoub et al. in their Full Paper on page 9757 ff., to efficiently and selectively functionalize cyclodextrins.

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  3. News

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  4. Concept

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    1. Geometric Formalism for DNA Quadruplex Folding (pages 9738–9745)

      Mateus Webba da Silva

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/chem.200701255

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      Quadruplex folding formalism—what four-stranded DNA topologies are possible? A formalism detailing the structural geometric basis for quadruplex topologies (see scheme) is described!

  5. Full Papers

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    1. Half-Sandwich Rhodium (and Iridium) Complexes as Enantioselective Catalysts for the 1,3-Dipolar Cycloaddition of 3,4-Dihydroisoquinoline N-Oxide to Methacrylonitrile (pages 9746–9756)

      Daniel Carmona, M. Pilar Lamata, Fernando Viguri, Ricardo Rodríguez, Fernando J. Lahoz and Luis A. Oro

      Version of Record online: 30 OCT 2007 | DOI: 10.1002/chem.200701140

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      Performance enhancement: By taking advantage of the knowledge of the relative abundance and stereochemistry of the active metallic intermediates present in the catalytic system (see scheme), a moderate enantioselectivity can be improved to achieve an excellent level of selection. In addition, such studies provide explanations for unexpected trends, the relationship between the configuration at the metal to the stereochemical outcome, and the efficient reutilization of the catalyst.

    2. Chemical Clockwise Tridifferentiation of α- and β-Cyclodextrins: Bascule-Bridge or Deoxy-Sugars Strategies (pages 9757–9774)

      Olivia Bistri, Pierre Sinaÿ, Jesùs Jiménez Barbero and Matthieu Sollogoub

      Version of Record online: 16 NOV 2007 | DOI: 10.1002/chem.200700971

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      Concave molecules desperately need to be efficiently polyhetero-functionalised to fulfil their promises. Bascule-bridging and deoxygenation of sugars are two complementary ways to reach an unprecedented degree of complexity of functionalisation of the primary rim of cyclodextrins (see scheme).

    3. Synchrotron X-Ray Charge-Density Study of Coordination Polymer [Mn(HCOO)2(H2O)2] (pages 9775–9790)

      Rasmus D. Poulsen, Mads R. V. Jørgensen, Jacob Overgaard, Finn K. Larsen, Wolfgang Morgenroth, Timothy Graber, Yu-Sheng Chen and Bo B. Iversen

      Version of Record online: 8 NOV 2007 | DOI: 10.1002/chem.200700756

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      Accuracy of charge-density measurements: X-ray charge-density analysis is used to investigate the covalent bonding features responsible for magnetic ordering in a Mn-based coordination polymer. Three different single-crystal X-ray diffraction data sets are obtained (see figure), and comparison with ab initio theory suggests that the 16 K APS data set provides the most accurate density.

    4. General Synthesis Route to Benanomicin-Pradimicin Antibiotics (pages 9791–9823)

      Minoru Tamiya, Ken Ohmori, Mitsuru Kitamura, Hirohisa Kato, Tadamasa Arai, Mami Oorui and Keisuke Suzuki

      Version of Record online: 28 SEP 2007 | DOI: 10.1002/chem.200700863

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      Total synthesis: A general synthetic route to the benanomicin-pradimicin antibiotics (BpAs) has been developed. Diastereoselective ring-opening of a biaryl lactone and the stereocontrolled semi-pinacol cyclization of an aldehyde acetal has led to the construction of the tetracyclic core of the aglycon, an ideal platform for the divergent access to various BpAs. Installation of an amino acid and glycosylation completed the total synthesis of benanomicin A (2a), benanomicin B (2b), and pradimicin A (1a).

    5. Tautomerism in Novel Oxocorrologens (pages 9824–9833)

      Yongshu Xie, Jonathan P. Hill, Amy Lea Schumacher, Paul A. Karr, Francis D'Souza, Christopher E. Anson, Annie K. Powell and Katsuhiko Ariga

      Version of Record online: 19 OCT 2007 | DOI: 10.1002/chem.200701428

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      Corrole tautomers: A novel oxocorrole derivative exhibits three-way NH/OH tautomerism (see picture; key: blue= corrole N atom; green=porphyrinogen-like N atom; red=substituent O atom) under control by solvent polarity. This tautomerism can be modulated by alkylation at one of the oxocorrole macrocyclic nitrogen atoms to yield a well-defined and more easily controlled two-way NH/OH tautomerism.

    6. Multifunctional “Clickates” as Versatile Extended Heteroaromatic Building Blocks: Efficient Synthesis via Click Chemistry, Conformational Preferences, and Metal Coordination (pages 9834–9840)

      Robert M. Meudtner, Marc Ostermeier, Richard Goddard, Christian Limberg and Stefan Hecht

      Version of Record online: 19 OCT 2007 | DOI: 10.1002/chem.200701240

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      “Clever clicking”: Attaching two triazole fragments to a central pyridine moiety provides a versatile platform with distinct conformational preferences and coordination behavior, leading to potential applications in materials chemistry (see scheme).

    7. Transition Metal Bisdithiolene Complexes Based on Extended Ligands with Fused Tetrathiafulvalene and Thiophene Moieties: New Single-Component Molecular Metals (pages 9841–9849)

      João P. M. Nunes, Mauro J. Figueira, Dulce Belo, Isabel C. Santos, Bruno Ribeiro, Elsa B. Lopes, Rui T. Henriques, Jose Vidal-Gancedo, Jaume Veciana, Concepció Rovira and Manuel Almeida

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/chem.200701050

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      Rare electrical conductors: The Au and Ni bisdithiolene complexes (an example of which is shown here) based on new, highly extended ligands that incorporate fused tetrathiafulvalene and thiophene moieties were prepared and characterised. These complexes in their neutral state present high electrical conductivities, and, in the case of [Ni(dtdt)2], can reach σRT≈250 S cm−1 with a clear metallic behaviour. These compounds are new examples of the still-rare single-component molecular metals.

    8. In Situ Synthesis of Gold and Silver Nanoparticles by Using Redox-Active Amphiphiles and Their Phase Transfer to Organic Solvents (pages 9850–9861)

      Satyabrata Si, Enakshi Dinda and Tarun K. Mandal

      Version of Record online: 24 OCT 2007 | DOI: 10.1002/chem.200701014

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      Small beginnings: A series of newly designed, redox-active amino acid based amphiphiles was used for the preparation of gold and silver nanoparticles by in situ reduction at basic pH (see scheme). The as-prepared amphiphile-coated metal nanoparticles can be efficiently transferred to different nonpolar organic solvents simply by acid treatment, without altering their native physicochemical properties and resulting in an increase in their thermal stability.

    9. A Borogermanate with Three-Dimensional Open-Framework Layers (pages 9862–9865)

      Ding-Bang Xiong, Jing-Tai Zhao, Hao-Hong Chen and Xin-Xin Yang

      Version of Record online: 15 OCT 2007 | DOI: 10.1002/chem.200701009

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      In the frame! A layered borogermanate with three-dimensional open-framework layers (see figure), K4[B8Ge2O17(OH)2], has been synthesized. It has the potential to eventually form nanocomposites with polymers and to be processed into thin microporous films.

    10. Enantioselective Total Synthesis of (+)-Ottelione A, (−)-Ottelione B, (+)-3-epi-Ottelione A and Preliminary Evaluation of Their Antitumor Activity (pages 9866–9881)

      Hiroshi Araki, Munenori Inoue, Takeyuki Suzuki, Takao Yamori, Michiaki Kohno, Kazuhiro Watanabe, Hideki Abe and Tadashi Katoh

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/chem.200700789

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      Ultrapotent antitumor agents! Otteliones A, B and 3-epi-ottelione A have been efficiently synthesized in enantiomerically pure forms starting from a known tetracyclic ketone. The cell growth inhibition profile, COMPARE analysis, and tubulin inhibitory assay demonstrated that unnatural 3-epi-ottelione A could be a promising candidate or a potential new lead for the development of anticancer agents targeting novel tubulin-binding sites.

    11. The Valence Problem of Pd4Br4Te3 (pages 9882–9891)

      Manuel Janetzky, Eva Rödel, Clemens Pietzonka, Ulrich Müller, Thorsten Ressler and Bernd Harbrecht

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/chem.200700658

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      A fractional oxidation state of −4/3 is indicated by relatively short Te[BOND]Te distances in Pd4Br4Te3. Physical property measurements and quantum chemical calculations substantiate the unusual oxidation state of tellurium in the title phase. As shown in the figure, Te atoms are arranged in triangles that form part of a pseudo cuboctahedral Pd6Br6Te6 unit.

    12. Ternary MgTiX-Alloys: A Promising Route towards Low-Temperature, High-Capacity, Hydrogen-Storage Materials (pages 9892–9898)

      Paul Vermeulen, Emile F. M. J. van Thiel and Peter H. L. Notten

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/chem.200700747

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      The future is hydrogen: MgyTizX(1−yz) (X=Al/Si) thin films were prepared by e-beam deposition. Hydrogen was inserted and extracted from these materials electrochemically. Isotherms of various composites were measured and showed that the thermodynamic properties of Mg-based hydrides can be regulated over a wide range by controlling the chemistry of the alloy.

    13. Alkali Metal Diphenylmethanides: Synthetic, Computational and Structural Studies (pages 9899–9911)

      Jacob S. Alexander, Damian G. Allis, Weijie Teng and Karin Ruhlandt-Senge

      Version of Record online: 21 SEP 2007 | DOI: 10.1002/chem.200700763

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      Contact molecule or separated ions? A convenient and effective synthetic route involving desilylation is presented for a family of alkali diphenylmethanides (see figure for example) allowing the in-depth study of factors governing ion association and metal–ligand binding preferences in solution and the solid state. Experimental studies are supplemented by detailed quantum chemical calculations.

    14. Stereochemical Consequences of Threefold Symmetry in Asymmetric Catalysis: Distorting C3 Chiral 1,1,1-Tris(oxazolinyl)ethanes (“Trisox”) in CuII Lewis Acid Catalysts (pages 9912–9923)

      Carole Foltz, Björn Stecker, Guido Marconi, Stéphane Bellemin-Laponnaz, Hubert Wadepohl and Lutz H. Gade

      Version of Record online: 23 OCT 2007 | DOI: 10.1002/chem.200701085

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      Threefold versus twofold symmetry in asymmetric catalysis: The conceptual differences become apparent in constructing new catalysts by systematically “deforming” the stereodirecting ligand, for example, by inverting chiral centres, and have been tested for the first time in CuII Lewis acid catalysis (see scheme).

    15. Structures with Tunable Strong Ferromagnetic Coupling: from Unordered (1D) to Ordered (Discrete) (pages 9924–9930)

      Yong-Fei Zeng, Jiong-Peng Zhao, Bo-Wen Hu, Xin Hu, Fu-Chen Liu, Joan Ribas, Jordi Ribas-Ariño and Xian-He Bu

      Version of Record online: 13 SEP 2007 | DOI: 10.1002/chem.200700637

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      Two birds with one stone: Although azido CuII complexes 1 and 2, synthesized under similar hydrothermal conditions, both show strong ferromagnetic coupling, discrete complex 2 exhibits long-range ferromagnetic ordering, while the very similar 1D system 1 does not. DFT calculations rationalized the strong ferromagnetic coupling, and the calculated spin densities on the magnetic orbitals of the bridged unit of 2 and the two different bridged moieties of 1 (see picture; Cu pink, N blue, O red, C green) can explain these features.

    16. Nanosized Ball Joints Constructed from C60 and Tribenzotriquinacene Sockets: Synthesis, Component Self-Assembly and Structural Investigations (pages 9931–9938)

      Björn Bredenkötter, Stefan Henne and Dirk Volkmer

      Version of Record online: 28 SEP 2007 | DOI: 10.1002/chem.200700915

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      Construction made smaller! Host–guest complexes that consist of a fullerene C60 guest molecule with tribenzotriquinacene-based hosts have been developed (see figure). The complex formed resembles a nanosized ball joint and represents the first member of a potential nanosized construction kit.

    17. Total Synthesis of the Proposed Structure of the Anthrapyran Metabolite δ-Indomycinone (pages 9939–9947)

      Lutz F. Tietze, Ramakrishna Reddy Singidi and Kersten M. Gericke

      Version of Record online: 21 SEP 2007 | DOI: 10.1002/chem.200700823

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      The first total synthesis of the proposed structure of the anthrapyran antibiotic δ-indomycinone has been accomplished (see scheme). The spectroscopic data obtained for the synthetic compounds are not in agreement with those reported for the natural product, and therefore, revision of the assigned structure is required.

    18. Amphiphilic and Magnetic Properties of a New Class of Cluster-Bearing [L2Cu44-O)(μ2-carboxylato)4] Soft Materials (pages 9948–9956)

      Rajendra Shakya, Sarmad Sahiel Hindo, Libo Wu, Suolong Ni, Marco Allard, Mary Jane Heeg, Sandro R. P. da Rocha, Gordon T. Yee, Hrant P. Hratchian and Cláudio N. Verani

      Version of Record online: 23 OCT 2007 | DOI: 10.1002/chem.200700875

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      Copper cluster films: An approach towards amphiphilic systems bearing multimetallic clusters (see figure) and their ability to form Langmuir–Blodgett films is presented. The Cu4 cluster is antiferromagnetically coupled and broken-symmetry DFT calculations are used to describe the main superexchange pathways involved in the whole cluster.

    19. A Theoretical Characterization of the Photoisomerization Channels of 1,2-Cyclononadienes on both Singlet and Triplet Potential-Energy Surfaces (pages 9957–9972)

      Ming-Der Su

      Version of Record online: 18 SEP 2007 | DOI: 10.1002/chem.200700646

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      Which route from an intersection? The ground-, 1(ππ*)-, and 3(ππ*)-state potential-energy surfaces of 1,2-cyclononadiene (shown here) and isomeric C9H14 species, as well as 1-methyl-1,2-cyclononadiene and isomeric C10H16 species, were all studied by the CAS/6–31G(d) method. Theoretical results were in good agreement with available experimental observations for both 1,2-cyclononadiene and 1-methyl-1,2-cyclononadiene isomerization reactions under singlet and triplet direct or sensitized irradiation.

    20. One-Pot Three-Component Catalytic Synthesis of Fully Substituted Pyrroles from Readily Available Propargylic Alcohols, 1,3-Dicarbonyl Compounds and Primary Amines (pages 9973–9981)

      Victorio Cadierno, José Gimeno and Noel Nebra

      Version of Record online: 14 SEP 2007 | DOI: 10.1002/chem.200701132

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      Putting the pieces together: A novel multicomponent approach to the synthesis of fully substituted pyrroles from readily accessible and inexpensive precursors has been developed (see scheme; dppf: 1,1′-bis(diphenylphosphanyl)ferrocene). This simple, general and efficient one-pot catalytic transformation allows the direct introduction of carbonyl functionalities onto the pyrrolic skeleton and also shows great tolerance to functional groups on the nitrogen-atom substituent.

    21. Ligand-Activated Lithium-Mediated Zincation of N-Phenylpyrrole (pages 9982–9989)

      Anne Seggio, Marie-Isabelle Lannou, Floris Chevallier, Daisuke Nobuto, Masanobu Uchiyama, Stéphane Golhen, Thierry Roisnel and Florence Mongin

      Version of Record online: 14 SEP 2007 | DOI: 10.1002/chem.200700608

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      Accessibility of lithium is a prerequisite for efficient metalation: The effect of solvents and lithium ligands on the outcome of zincation reactions was examined and the reaction pathway and mechanism were discussed on the basis of theoretical calculations (see picture).

    22. Strong Stacking between F⋅⋅⋅H[BOND]N Hydrogen-Bonded Foldamers and Fullerenes: Formation of Supramolecular Nano Networks (pages 9990–9998)

      Chuang Li, Yuan-Yuan Zhu, Hui-Ping Yi, Chang-Zhi Li, Xi-Kui Jiang, Zhan-Ting Li and Yi-Hua Yu

      Version of Record online: 21 SEP 2007 | DOI: 10.1002/chem.200701047

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      Tightly held: Strong interactions between F⋅⋅⋅H[BOND]N hydrogen-bonded foldamers and fullerenes have been identified, and have been utilized to create nanoscaled supramolecular networks (see figure).

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      Preview: Chem. Eur. J. 36/2007 (page 10003)

      Version of Record online: 27 NOV 2007 | DOI: 10.1002/chem.200790134

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